CN101826645B - Reversible air battery using piperidine as hydrogen storage media - Google Patents
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Abstract
The invention relates to a reversible air battery, which aims at providing a reversible air battery using piperidine as hydrogen storage media. The reversible air battery adopts piperidine as a hydrogen storage media and also as negative electrode active substance, a proton exchange membrane as an electrolyte, and an air electrode as a positive electrode. When the negative electrode discharges, the piperidine is electrochemically oxidized to generate pyridine. During charging, the pyridine is electrochemically reduced to generate the piperidine. Compared with a traditional regenerated hydrogen-oxygen fuel battery, by using the piperidine as the hydrogen storage media, the invention can greatly improve the specific capacity of the battery, and can realize large-scale commercial application. The piperidine reversible air battery can be used as a portable and mobile power supply for electric automobiles, electronic products, military equipment and the like. The piperidine reversible air battery can be made into a semienclosed type battery, i.e. the fuel side is sealed, and the air side is opened. The invention can solve the safety problem caused by the defect of full open type of the traditional fuel battery, and can greatly improve the practicability of the fuel battery.
Description
Technical field
The present invention relates to a kind of reversible air battery, more particularly, the present invention relates to a kind of with piperidines as hydrogen storage media, PEM is electrolytical reversible air battery.
Background technology
Hydrogen energy source cleaning, environmental friendliness, renewable are considered to optimal secondary energy sources of 21 century.The reversible hydrogen oxygen cell is commonly called as the regenerated hydrogen oxygen fuel cell, but is a kind of device of realizing energy efficient inverse conversion between Hydrogen Energy and the electric energy.Regenerated hydrogen oxygen fuel cell gravimetric specific energy height, long service life, good reliability cause the extensive concern of countries in the world.
The hydrogen that produces at negative pole when the conventional regeneration hydrogen oxygen fuel cell stores charging with the mode of High Pressure Hydrogen; Though PEM is that electrolytical fuel cell (PEMFC) technology reaches its maturity, yet its commercialization also faces an insoluble problem: the production of hydrogen and accumulating.The accumulating of hydrogen mainly contains dual mode: the first, and gas cylinder storage hydrogen, shortcoming is that volumetric specific energy is low, and is high to equipment requirements, and has certain potential safety hazard; The second, utilize reformation gas to give the fuel cell charging, this must make fuel cell system complicated, increases cost, is difficult to as portable or portable power source.
People attempt seeking other alternative fuel to overcome the technology barrier of PEMFC, and are wherein in the majority with organic molecule.For DMFC, there is not the problem of accumulating difficulty in fuel, but reactivity is low and very easily make the infiltration between negative electrode and anode of catalyst poisoning, especially methyl alcohol can cause the heavy losses of battery performance.Research to direct alcohol fuel cell shows, has the C-C key in the molecular structure of ethanol, thereby its thorough electrochemical oxidation is generated CO
2Very difficulty can generate various accessory substances in this process, in addition usually such as aldehyde and ester.For avoiding molecular structure to have the C-C key; Someone attempts using dimethoxymethane (DMM) and trimethoxy-methane (TMM) to act as a fuel; But have methyl alcohol to generate behind two kinds of oxidation operations, still do not solve the problem that fuel infiltration causes battery performance to reduce, preparation cost is also than higher; Formic acid and formaldehyde are lower as the energy density of battery fuel, and formic acid has corrosivity, the formaldehyde unstable chemcial property, and the both is toxic in addition.So all there is the problem on technology, economy or the safety in the direct fuel cell that these organic molecules act as a fuel.
Piperidines, the another name hexahydropyridine is a heterocyclic compound, molecular formula is (CH
2)
5NH.It is a secondary amine, can regard carbon of cyclohexane as and substituted the compound that the back forms, i.e. piperidine by nitrogen.In the industry, it makes catalyst by pyridine hydrogenation preparation with molybdenum bisuphide:
Also can pyridine be reduced to piperidines with sodium-ethanolic solution.The piperidines that forms can generate pyridine through dehydrogenation.Pyridine is the 6-membered heterocyclic compound that contains a nitrogen heteroatom.Can regard (CH) in the benzene molecular as by the substituted compound of N, so claim pyridine again.
Through the method for electrochemical redox, can realize the mutual conversion between piperidines and the pyridine, during as negative electrode active material, its negative pole discharges and recharges reaction as follows with piperidines:
As active material, it discharges and recharges reaction as follows to side of the positive electrode with water:
The electrochemical reaction of comprehensive both positive and negative polarity, the cell reaction of piperidines reversible air battery is:
The hydrogen content of piperidines is very high, is 12.9wt.%.Effective hydrogen storage content between piperidines and pyridine is 7wt.%, and the specific capacity of piperidines can reach 1.89Ah/g, is far longer than the hydrogen bearing alloy specific capacity used in the nickle/metal hydrides battery (0.25～0.4Ah/g), so piperidines is a kind of hydrogen storage media efficiently.
From the molecular structure angle; There is stable, firm aromatic rings in the piperidines molecule; Carbon and nitrogen on the ring are not easy oxidation; Therefore the hydrogen that the electrochemical oxidation of piperidines can only oxidized portion can not make the aromatic rings open loop, can not form the intermediate product with carbonyl structure that electrochemical oxidation reactions produces yet.The molecular structure symmetry, dipole moment is less, can effectively reduce piperidines and H
3 +Combination between the O reduces the fuel infiltration that the electricity towing causes.
Piperidines is an achromaticity and clarification liquid under the normal temperature and pressure, and fusing point is-7 ℃, and boiling point is 106 ℃, is easy to transportation and storage.Pyridine also is an achromaticity and clarification liquid under the normal temperature and pressure, and fusing point is-41.6 ℃, and boiling point is 115.3 ℃, through the crystallisation or the way of distillation, is easy to separate.Piperidines and pyridine are all water-soluble, ethanol, ether etc., form azeotropic compound with water.The act as a fuel fuel of battery both can be implemented liquid feed, also can implement gaseous feed, was convenient to the system design of fuel cell.Be made into semi-enclosed battery, promptly fuel-side is airtight, and air side is open, can overcome the safety issue that drawback caused of conventional fuel cell full open model.Be highly suitable for as carry, the fuel cell of portable power source, be expected to become a kind of high-capacity power supply.Can be widely used in the products for civilian use such as mobile phone, camera, video camera, cordless power tool, emergency power supply, electric automobile, also can be applicable to Aeronautics and Astronautics, military fields such as individual combat, unmanned plane.
Summary of the invention
The technical problem that the present invention will solve is, overcomes deficiency of the prior art, and providing a kind of is hydrogen storage media with the piperidines, and PEM is electrolytical piperidines reversible air battery, improves the volume and capacity ratio of reversible fuel cell with this.
For solving the problems of the technologies described above, technical scheme of the present invention is:
Providing a kind of is the reversible air battery of hydrogen storage media with the piperidines, and it is hydrogen storage media and as negative electrode active material, PEM is an electrolyte that this reversible air battery adopts piperidines, and air electrode be a positive pole.Piperidines is generated pyridine by electrochemical oxidation during negative discharge.Pyridine is generated piperidines by electrochemical reduction during charging.
Among the present invention, the negative electrode active material of reversible air battery is the aqueous solution of piperidines or piperidines is dissolved in the acid solution gained that said acid solution is 1～6M L
-1Sulfuric acid or phosphoric acid; Piperidines concentration in the piperidines aqueous solution or the nipecotic acid solution is 0.5～10M L
-1
Among the present invention; Reversible air battery is as anode catalyst or cathode catalyst with noble metal or precious metal alloys; Said noble metal or precious metal alloys are expressed as with general formula: ABx; A is any one among precious metals pt, Pd, Au, Os or the Ag, and B is any one among Pt, Pd, Au, Os, Ag, Fe, Co, Ni, Mn, Mo, Sn or the Cu; The excursion of x is 0～1.
Among the present invention, reversible air battery is to be the body that supports of anode catalyst or cathode catalyst with the polypyrrole modifying material with carbon element, and described material with carbon element is any one in CNT (CNT), carbon black (CB), carbon nano rod (CNR), the carbon nanocoils (CNW).
Among the present invention; The preparation method of the positive pole of reversible air battery is: with the perfluorinated sulfonic resin liquid of polypyrrole modifying carbon supported noble metal or polypyrrole modifying carbon supported noble metal alloy catalyst, water, 5wt.%, absolute ethyl alcohol according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation form slurry; Be coated on carbon paper or carbon cloth that hydrophobic is handled, dry naturally and get final product.
Among the present invention; The preparation method of the negative pole of reversible air battery is: with the perfluorinated sulfonic resin liquid of polypyrrole modifying carbon supported noble metal or polypyrrole modifying carbon supported noble metal alloy catalyst, water, 5wt.%, absolute ethyl alcohol according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation form slurry; Be coated on the carbon paper or carbon cloth of hydrophilic treatment, dry naturally and get final product.
Among the present invention, reversible air battery has the following structure of arranging successively in a lateral direction: negative plates, negative pole matrix, cathode catalyst layer, PEM, anode catalyst layer, anodal matrix and anode plate; Sealing is all realized with sealing ring in the two ends up and down of fuel cell, and its negative terminal is drawn by negative plates, and positive terminal is drawn by anode plate; Constitute the flow of solution that the negative pole runner is used for piperidines between negative plates and the negative pole matrix, the piperidine solution inlet is established on the top of negative pole runner, and the negative pole outlet is established in its bottom; Constitute the circulation that anodal runner is used for air between anode plate and the anodal matrix, air intake is established on the top of anodal runner, and anodal outlet is established in its bottom.
Among the present invention, said negative pole matrix is carbon paper or the carbon cloth through hydrophilic treatment, and said anodal matrix is carbon paper or the carbon cloth of handling through hydrophobic.
Among the present invention, institute's cathode catalyst layer or anode catalyst layer are: the slurry that the perfluorinated sulfonic resin liquid of polypyrrole modifying carbon supported noble metal or polypyrrole modifying carbon supported noble metal alloy catalyst, water, 5wt.%, absolute ethyl alcohol become according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation.
Compared with prior art, the invention has the beneficial effects as follows:
Than the conventional regeneration hydrogen oxygen fuel cell; Piperidines can be improved the specific capacity of battery greatly as hydrogen storage media, can carry out the large-scale commercial applications application, said piperidines reversible air battery can be used as portable and portable power supply; Like electric automobile, electronic product and military equipment etc.
The piperidines reversible air battery can be made into semi-enclosed battery, and promptly fuel-side is airtight, and air side is open, can overcome the safety issue that drawback caused of conventional fuel cell full open model, improves the practicality of fuel cell greatly.
Than the conventional carbon supported noble metal catalyst; Adopt polypyrrole modifying carbon supported noble metal or precious metal alloys as catalyst; Polypyrrole on material with carbon element can make the distribution disperse more of catalyst particle, evenly; Particle size is more tiny, helps to improve activity of such catalysts, improves the charge-discharge performance of piperidines reversible air battery.
Figure of description
Fig. 1 is the structure of said piperidines reversible air battery and the conversion between when discharge material.
The charging and discharging curve of the said piperidines reversible air battery of Fig. 2.
Reference numeral among Fig. 1 is:
1 negative pole runner, 2 negative pole matrixes, 3 cathode catalyst layers, 4 PEMs, 5 anode catalyst layers, 6 anodal matrixes, 7 sealing rings, 8 anode plates, 9 negative plates, 10 piperidine solution inlet, 11 air intakes, 12 negative pole outlets, 13 anodal outlets, 14 anodal runners.
Reference numeral among Fig. 2 is: the discharge curve of 1. said piperidines reversible air battery, the 2. charging curve of said piperidines reversible air battery.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Among the present invention; The preparation method of polypyrrole modifying material with carbon element can consult the introduction of the application inventor in Chinese invention patent application CN101549304, and the preparation method of polypyrrole modifying carbon supported noble metal catalyst or polypyrrole modifying carbon supported noble metal alloy catalyst can consult the introduction of the application inventor in Chinese invention patent application (application number 201010039824.1 and 201010132183.4).The present invention is not described in detail foregoing, only enumerate with regard to the part examples of implementation, but cited content can not to be regarded as be the restricted statement content to method.
Embodiment 1: the preparation of polypyrrole modifying carbon supported noble metal catalyst
Material with carbon element 1～10 gram is distributed to is made into suspension-turbid liquid in the water, its mass ratio is 1: 15; Adding glacial acetic acid adjusting pH value is 2.5, stirring at room 10min; Mass ratio by material with carbon element and pyrroles is that 1: 0.05 adding pyrroles stirs 5min, adds chloride 1～5 gram of above noble metal then; The H that adds 0.05 gram mass behind the stirring at room 3h again
2O
2Behind the stirring at room 3h, be heated to 70 ℃; Slowly adding 300ml concentration is 0.1M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 30min, natural cooling; After filtering with deionized water wash, behind 70 ℃ of dry 6h of vacuum under the Ar inert atmosphere 300 ℃ of insulation 5h heat-treat, make the polypyrrole modifying carbon supported noble metal catalyst, the loading of its noble metal is listed in table 1.
The relation of noble metal loading and material with carbon element and precious metal chloride addition in the table 1 polypyrrole modifying carbon supported noble metal catalyst
Embodiment 2: the preparation of polypyrrole modifying carbon supported noble metal alloy catalyst
Material with carbon element 100～2000 gram is distributed to is made into suspension-turbid liquid in the water, its mass ratio is 1: 15; Adding the salt acid for adjusting pH value is 3, stirring at room 30min; Mass ratio by carbon black and pyrroles is that 1: 0.3 adding pyrroles stirs 10min, presses the chloride that table 2 adds respective element and corresponding amount then; The H that adds 100 gram masses behind the stirring at room 10h again
2O
2Behind the stirring at room 10h, be heated to 90 ℃; Slowly adding 3000ml concentration is 0.3M L
-1Reducing agent alkalescence sodium borohydride solution after, vigorous stirring 60min, natural cooling; After filtering with deionized water wash, behind 90 ℃ of dry 12h of vacuum at N
2The following 600 ℃ of insulation 1h of atmosphere heat-treat, and make polypyrrole modifying carbon supported noble metal alloy catalyst, and the atomic ratio of alloying element is listed in table 2 in the catalyst.Catalyst content is 6～67wt.%.
The atom of alloying element catalyst content when in the table 2 polypyrrole modifying carbon supported noble metal alloy catalyst
Embodiment 3: the both positive and negative polarity preparation
With perfluorinated sulfonic resin (Nafion) solution of the polypyrrole modifying carbon supported noble metal that obtains or precious metal alloys catalyst, water, 5wt.% and absolute ethyl alcohol according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation form slurry; Be coated on the carbon paper or carbon cloth of hydrophilic treatment, make negative pole after drying naturally; Slurry is coated on carbon paper or carbon cloth that hydrophobic is handled, makes positive pole after drying naturally.The loading of catalyst is 1～67mg cm
-2
The loading of catalyst in table 3 both positive and negative polarity preparation prescription and the electrode
Embodiment 4: the discharge of piperidines reversible air battery
With anodal (the catalyst loading amount: 11.05mg cm of the Pt/PPy-CNW that is coated on carbon paper of preparation among the embodiment 3
-2), be coated on the AuCo of carbon paper
0.6/ PPy-CNT negative pole (catalyst loading amount: 1.73mg cm
-2) separate with Nafion 112 films, dress up the piperidines reversible air battery by the structural group of Fig. 1.
Press table 4 preparation piperidine solution as negative electrode active material, piperidines concentration is 0.5～10M L
-1, working temperature is set in 0～100 ℃, negative pole flow velocity 1ml min
-1, air velocity 5ml min
-1, 10～100 ℃ of current density 100mA of air wetting temperature cm
-2Constant current discharge, the discharge capacity of the open circuit voltage that obtains, power density and piperidines is listed in table 4.
The discharge capacity of table 4 piperidines reversible air battery open circuit voltage, power density and piperidines and the relation of temperature and piperidine solution composition
Can find out that from table 4 piperidines in sulfuric acid or phosphoric acid solution, has reactivity preferably, the raising of working temperature and air wetting temperature helps to improve the performance of piperidines reversible air battery.
Embodiment 5: the piperidines reversible air battery discharges and recharges
With anodal (the catalyst loading amount: 66.3mg cm of the Pt/PPy-CNW that is coated on carbon cloth of preparation among the embodiment 3
-2), be coated on the AuCo of carbon cloth
0.6/ PPy-CNT negative pole (catalyst loading amount: 10.4mg cm
-2) separate with Nafion 117 films, dress up the piperidines reversible air battery by the structural group of Fig. 1.
The side of the positive electrode aerating oxygen is dissolved in 1M L with piperidines
-1Sulfuric acid in be mixed with piperidine solution (piperidines concentration be 2M L
-1) as negative electrode active material, working temperature is set at 80 ℃, negative pole flow velocity 5ml min
-1, air velocity 5ml min
-1, 80 ℃ of air wetting temperature, current density 200mA cm
-2Implement constant current discharge, the negative side piperidines is converted into pyridine, and side of the positive electrode obtains water.Discharge after 8 hours, feed water at positive pole, with 200mA/cm
2The current density constant current charge, the negative side pyridine is converted into piperidines, side of the positive electrode effusion oxygen.The charging and discharging curve of said battery when Fig. 2 is 80 ℃ of working temperatures.
Embodiment 6: the composition of speed capabilities and catalyst loading amount, piperidine solution and the relation of concentration
The positive pole and the negative pole of preparation among the embodiment 3 are separated with Nafion 112 films, dress up the piperidines reversible air battery by the structural group of Fig. 1.
With piperidines and concentration is 1～6M L
-1Sulfuric acid or phosphoric acid mix, be modulated into acid piperidine solution as negative electrode active material, the side of the positive electrode aerating oxygen, working temperature is set at 100 ℃, negative pole flow velocity 10ml min
-1, air velocity 10ml min
-1, 100 ℃ of air wetting temperature are with 300mA/cm
2Current density discharge and recharge; (parameter of piperidines speed capabilities is weighed in C °=ratio (C/C °) conduct 1.89Ah/g) to the theoretical specific capacity of resulting discharge capacity and piperidines; Its ratio is more near 1; The catalytic activity that cathode catalyst is described is high more, and employed solvent can be strengthened the electrochemical oxidation dynamic performance of piperidines.Table 5 has provided the influence to the electrochemical oxidation dynamic performance of piperidines of catalyst and solvent composition and concentration.
Table 5 catalyst and solvent composition and concentration are to the influence of piperidines air cell speed capabilities
Embodiment 7: the reversible air battery among the present invention has following structural configuration:
Reversible air battery has the following structure of arranging successively in a lateral direction: negative plates 9, negative pole matrix 2, cathode catalyst layer 3, PEM 4, anode catalyst layer 5, anodal matrix 6 and anode plate 8; Sealing is all realized with sealing ring 7 in the two ends up and down of battery, and its negative terminal is drawn by negative plates 9, and positive terminal is drawn by anode plate 8; Constitute the flow of solution that negative pole runner 1 is used for piperidines between negative plates 9 and the negative pole matrix 2, piperidine solution inlet 10 is established on the top of negative pole runner 1, and negative pole outlet 12 is established in its bottom; Constitute the circulation that anodal runner 14 is used for air between anode plate 8 and the anodal matrix 6, air intake 11 is established on the top of anodal runner 14, and anodal outlet 13 is established in its bottom.
Said negative pole matrix 2 is carbon paper or carbon cloth through hydrophilic treatment, and said anodal matrix 6 is carbon paper or the carbon cloth of handling through hydrophobic.Institute's cathode catalyst layer 3 or anode catalyst layer 5 are slurries that the perfluorinated sulfonic resin liquid, absolute ethyl alcohol of polypyrrole modifying carbon supported noble metal or polypyrrole modifying carbon supported noble metal alloy catalyst, water, 5wt.% becomes according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation.
When reversible air battery discharged, piperidine solution got into negative side through the piperidine solution inlet 10 on negative plates 9 tops; Piperidines diffuses through negative pole matrix 2 and arrives cathode catalyst layer 3; Piperidines generation electrochemical oxidation generates proton and pyridine on catalyst; Proton is transferred to anode catalyst layer 5 through PEM 4; Proton and airborne oxygen generation electrochemical reducting reaction generate water on catalyst, and water is discharged from outlet 13 through anodal anodal runner 14; Pyridine is discharged through the negative pole outlet 12 of negative pole bottom, and is as shown in Figure 1.
Among the present invention, when charging, generate oxygen and proton at anodal water generation electrochemical oxidation to reversible air battery.Proton is transferred to negative pole through PEM; Pyridine and proton generation electrochemical reduction generate piperidines on negative pole, and piperidines is discharged through the negative pole outlet 12 of bottom.
At last, it is also to be noted that what more than enumerate only is specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (9)
1. one kind is the reversible air battery of hydrogen storage media with the piperidines, it is characterized in that, this reversible air battery is hydrogen storage media and as negative electrode active material, PEM is an electrolyte with the piperidines, and air electrode is anodal.
2. reversible air battery according to claim 1 is characterized in that, the negative electrode active material of this reversible air battery is the aqueous solution of piperidines or piperidines is dissolved in the acid solution gained that said acid solution is 1～6mol L
-1Sulfuric acid or phosphoric acid; The concentration of the piperidines in the piperidines aqueous solution or the nipecotic acid solution is 0.5～10mol L
-1
3. according to the reversible air battery of claim 1 or 2 described in any one; It is characterized in that; This reversible air battery is as anode catalyst or cathode catalyst with noble metal or precious metal alloys; Said noble metal or precious metal alloys are expressed as with general formula: ABx, A are any one among precious metals pt, Pd, Au, Os or the Ag, and B is any one among Pt, Pd, Au, Os, Ag, Fe, Co, Ni, Mn, Mo, Sn or the Cu; The excursion of x is 0～1.
4. reversible air battery according to claim 3; It is characterized in that; This reversible air battery is to be the body that supports of anode catalyst or cathode catalyst with the polypyrrole modifying material with carbon element, and described material with carbon element is any one in CNT, carbon black, carbon nano rod or the carbon nanocoils.
5. reversible air battery according to claim 3; It is characterized in that; The preparation method of the positive pole of this reversible air battery is: with the perfluorinated sulfonic resin liquid of polypyrrole modifying carbon supported noble metal or polypyrrole modifying carbon supported noble metal alloy catalyst, water, 5wt.%, absolute ethyl alcohol according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation form slurry; Be coated on carbon paper or carbon cloth that hydrophobic is handled, dry naturally and get final product.
6. reversible air battery according to claim 3; It is characterized in that; The preparation method of the negative pole of this reversible air battery is: with the perfluorinated sulfonic resin liquid of polypyrrole modifying carbon supported noble metal or polypyrrole modifying carbon supported noble metal alloy catalyst, water, 5wt.%, absolute ethyl alcohol according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation form slurry; Be coated on the carbon paper or carbon cloth of hydrophilic treatment, dry naturally and get final product.
7. reversible air battery according to claim 1; It is characterized in that this reversible air battery has the following structure of arranging successively in a lateral direction: negative plates, negative pole matrix, cathode catalyst layer, PEM, anode catalyst layer, anodal matrix and anode plate; Sealing is all realized with sealing ring in the two ends up and down of battery, and its negative terminal is drawn by negative plates, and positive terminal is drawn by anode plate; Constitute the flow of solution that the negative pole runner is used for piperidines between negative plates and the negative pole matrix, the piperidine solution inlet is established on the top of negative pole runner, and the negative pole outlet is established in its bottom; Constitute the circulation that anodal runner is used for air between anode plate and the anodal matrix, air intake is established on the top of anodal runner, and anodal outlet is established in its bottom.
8. reversible air battery according to claim 7 is characterized in that, said negative pole matrix is carbon paper or the carbon cloth through hydrophilic treatment, and said anodal matrix is carbon paper or the carbon cloth of handling through hydrophobic.
9. reversible air battery according to claim 7; It is characterized in that institute's cathode catalyst layer or anode catalyst layer are: the slurry drying thing that the perfluorinated sulfonic resin liquid of polypyrrole modifying carbon supported noble metal or polypyrrole modifying carbon supported noble metal alloy catalyst, water, 5wt.%, absolute ethyl alcohol form according to 1: 3: 2～7: 3～6 mass ratio hybrid modulation.
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| CN102800878B (en) * | 2011-05-27 | 2015-04-22 | 中国地质大学（武汉） | Integrated direct fuel cell energy storing and supplying system based on liquid hydrogen storage material |
| CN102800877B (en) * | 2011-05-27 | 2014-09-17 | 中国地质大学（武汉） | Parallel direct fuel cell energy storage and supply system based on liquid hydrogen storage material |
| CN102800880A (en) * | 2011-05-27 | 2012-11-28 | 中国地质大学（武汉） | Direct fuel cell based on organic liquid hydrogen storage material |
| WO2017004777A1 (en) | 2015-07-06 | 2017-01-12 | SZ DJI Technology Co., Ltd. | Systems and methods for uav fuel cell |
| CN108675404B (en) * | 2018-05-17 | 2020-08-18 | 华南师范大学 | Method for continuous low-energy-consumption desalting by using redox reaction of fluid battery and application of method |
| CN110767913B (en) * | 2019-11-07 | 2022-06-21 | 安徽师范大学 | Single silver-palladium alloy nanowire electrode and preparation method and application thereof |
| CN113140840B (en) * | 2021-05-18 | 2022-09-30 | 中国科学技术大学 | Aqueous conductive polymer-hydrogen secondary battery |
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| CN101147286A (en) * | 2005-08-25 | 2008-03-19 | 松下电器产业株式会社 | Electrode for use in oxygen reduction |
| CN101405897A (en) * | 2006-03-22 | 2009-04-08 | 吉莱特公司 | Zinc/air cell |
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| CN101147286A (en) * | 2005-08-25 | 2008-03-19 | 松下电器产业株式会社 | Electrode for use in oxygen reduction |
| CN101405897A (en) * | 2006-03-22 | 2009-04-08 | 吉莱特公司 | Zinc/air cell |
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