CN102800880A - Direct fuel cell based on organic liquid hydrogen storage material - Google Patents
Direct fuel cell based on organic liquid hydrogen storage material Download PDFInfo
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- CN102800880A CN102800880A CN2011101391738A CN201110139173A CN102800880A CN 102800880 A CN102800880 A CN 102800880A CN 2011101391738 A CN2011101391738 A CN 2011101391738A CN 201110139173 A CN201110139173 A CN 201110139173A CN 102800880 A CN102800880 A CN 102800880A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a direct fuel cell, and in particular relates to a direct fuel cell based on an organic liquid hydrogen storage material. The direct fuel cell comprises a fuel cell single unit, wherein the fuel cell single unit is connected with a load by an AC/DC conversion circuit. The direct fuel cell is characterized in that a hydrogen storage material outlet on the fuel cell single unit is communicated with a hydrogen storage material tank by a hydrogen storage material output pipe; a hydrogen storage material hydride input hole on the fuel cell single unit is communicated with a hydrogen storage material hydride tank by a hydrogen storage material hydride input pipe; a hydrogen storage material hydride pump is arranged on the hydrogen storage material hydride input pipe; a water outlet on the fuel cell single unit is communicated with a water tank by a water outlet pipe; a gas inlet on the fuel cell single unit is communicated with an oxygen inlet pipe; a gas outlet is arranged at the top of the water tank; and the hydrogen storage material tank is filled with the hydrogen storage material which is multi-element mixed liquid unsaturated heterocyclic aromatic hydrocarbon. The direct fuel cell not only simplifies the devices (has simple structure) but also greatly improves the safety.
Description
Technical field
The present invention relates to Hydrogen Energy utilization technology in clean energy resource and the new energy field.Be specifically related to a kind of direct fuel cell based on liquid hydrogen storage material.Promptly, be translated into hydrogen storage material, emit electric energy simultaneously through direct fuel cell to the hydride of particular liquid hydrogen storage material.
Background technology
The energy is the basis that modern society depends on for existence and development, and the supply capacity substantial connection of the energy the sustainable development of national economy, is one of strategy basis of national security guarantee.Because rapid development of economy causes traditional non-renewable fossil fuel equal energy source to be in an emergency day by day, countries nowadays government all places hope on emerging energies such as Hydrogen Energy, solar energy, wind energy.
Fuel cell is a kind of Hydrogen Energy utilization technology of clean environment firendly.It utilizes the combustion reaction of fuel, and chemical energy is converted into electric energy, and without Carnot Engine, thereby have higher energy conversion efficiency.Fuel cell mainly is divided into SOFC (SOFC), molten carbonate fuel cell (MCFC), phosphoric acid type fuel cell (PAFC), alkaline fuel cell (AFC) and Proton Exchange Membrane Fuel Cells (PEMFC).Wherein Proton Exchange Membrane Fuel Cells and alkaline fuel cell working temperature lower (＜150 ℃) are called as low-temperature fuel cell, have application promise in clinical practice.At present, the fuel of low-temperature fuel cell is mainly H2, also can be pure micromolecular, like methyl alcohol etc.The fuel cell that uses methyl alcohol to act as a fuel is called as the direct fuel cell of methyl alcohol (DMFC), because methyl alcohol is liquid at normal temperatures, makes that the volume of fuel cell table is new, compares with gaseous fuel, and methyl alcohol is easy to deposit and transportation, has higher energy conversion efficiency.Its operation principle is following:
Anode: CH
3OH+H
2O → CO
2+ 6H
++ 6e
-
Negative electrode: 1.5O
2+ 6H
++ 6e
-→ 3H
2O
Overall reaction: CH
3OH+1.5O
2+ H
2O → CO
2+ 3H
2O
Can find out that from above-mentioned reaction methyl alcohol fuel methanol that direct fuel cell uses is running stores, a small amount of CO is still arranged in the product
2
The more hydrogen storage material of research comprises physical absorption class material and chemisorbed class material at present, and wherein the organic liquid hydrogen storage material is a kind of hydrogen storage material of potentialization.With the aromatic is example, and 1 mole of cyclohexane can be emitted 3 mol of hydrogen, generates 1 mole of benzene simultaneously; And benzene can pass through catalytic hydrogenation, again with storing hydrogen.The organic liquid hydrogen storage material is mainly liquid state at normal temperatures simultaneously, convenient transportation.At present people also concentrate on catalysis organic liquid hydrogen storage material releasing hydrogen gas such as using noble metal catalyst such as Pt, Pd, Ru for the research of organic liquid hydrogen storage material and supply fuel cell to use.
The temperature conditions of the kind of the aromatic molecules of being selected for use among the present invention and physical state thereof, certain embodiments and energy loss thereof etc. all have obvious difference with the research molecule of having reported, do concrete analysis discussion in the face of this down.
1) molecule must be not volatile liquid under working temperature (＜150 ℃), rather than solid.Though in certain solvent, solvent can be to reduce its concentration at electrode surface, just can not be as its working media like volatile liquid such as solids such as phenanthrene, anthracene and benzene for some solid dissolvable;
2) desorption temperature of hydrogenation molecule should not be too high, like the hydrogenation molecule cyclohexane dehydrogenation temperature of benzene greater than 300 ℃, this head and shoulders above the working temperature of battery, should not make the work medium; Simultaneously, if the dehydrogenation hydrogenation temperature is high, thereby the serious polarization of galvanic anode increases the energy loss in the dehydrogenation discharge.High like desorption temperature, the aromatic ring micromolecule such as benzene that institute's calorific requirement is big just should not be made the work medium.Unstable molecule as vinyl alcohol can not be as working media in addition.
Based on above factor, be necessary to research and develop the novel liquid that under working temperature, is at least, the organic liquid hydrogen storage material that its hydride desorption temperature is also enough low provides a kind of simple in structure, novel direct fuel cell.
Summary of the invention
The object of the present invention is to provide a kind of direct fuel cell based on the organic liquid hydrogen storage material, this direct fuel cell has characteristic of simple structure.
For realizing above-mentioned purpose, the technical scheme that the present invention taked is: a kind of direct fuel cell based on the organic liquid hydrogen storage material, and it comprises fuel cell 26, fuel cell 26 links to each other with load through the AC/DC change-over circuit; It is characterized in that: hydrogen storage material on the fuel cell 26 outlet 14 is connected with hydrogen storage material jar 17 by hydrogen storage material efferent duct 16; Hydrogen storage material hydride input port 13 on the fuel cell 26 is connected with hydrogen storage material hydride jar 18 by hydrogen storage material hydride input pipe 20, and hydrogen storage material hydride input pipe 20 is provided with hydrogen storage material hydride pump 19; Delivery port 25 on the fuel cell 26 is connected with water pot 22 by outlet pipe 24, the air inlet 21 on the fuel cell 26 with advance oxygen hose and be connected; Gas outlet 23 is arranged at water pot 22 tops; Fill hydrogen storage material in the hydrogen storage material jar 17, said hydrogen storage material is a multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons.
Described multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons is specially any one or any mixing more than two kinds in a plurality of liquid unsaturated heterocycle aromatic hydrocarbon molecules (as: carbazole, N-methyl carbazole, N-ethyl carbazole, indoles, quinoline etc.), and any is any proportioning when mixing more than two kinds.
Heterocycle in the described liquid unsaturated heterocycle aromatic hydrocarbon molecule can be that all rings are heterocycle, also part heterocycle, and hetero-atom total quantity scope is 1 to 20; Heterocycle and aromatic ring total quantity are 1 to 20; The carbon atom number is 4 to 10 in the single ring in the liquid unsaturated heterocycle aromatic hydrocarbon molecule.
Hetero-atom in the heterocycle be in nitrogen, oxygen, the sulphur etc. any one or any more than two kinds.
Liquid unsaturated heterocycle aromatic hydrocarbon molecule is carbazole, N-methyl carbazole, N-ethyl carbazole, indoles or quinoline etc.
Working media: hydrogen storage material of the present invention (being working media) is heteroatomic multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons (number of rings is 1 to 20) such as nitrogenous, oxygen, sulphur in the ring.On aromatic ring, contain the mixture liquid hydrogen storage material that different side groups form serial thick mixing/aromatic ring aromatic hydrocarbons.Wherein thick assorted/aromatic ring aromatic hydrocarbons number of rings was less than 8 o'clock, its existence form is single organic molecule; Number of rings is 8～15 o'clock, and its form is an oligomer; Number of rings surpasses at 15 o'clock, and its form is a conjugated polymer.Research shows that the condensed-nuclei aromatics number of rings is many more, and its hydrogenation molecule desorption temperature is lower, and corresponding dehydrogenation is consumed energy also fewer, but its fusing point is higher.In addition, if also contain hetero-atom in the ring, then the desorption temperature of condensed-nuclei aromatics hydride also can further reduce, but its fusing point also can further raise.If as hydrogen storage material, the electrolytic cell of above-mentioned direct electrolytic hydrogenation reaction (1) and the direct fuel coupling of R-of dehydrogenation exoelectrical reaction (2) can be constituted a kind of energy storage energy supply integral system based on Hydrogen Energy with multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons.This system works medium (multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons) reusable edible, zero discharge, environmental friendliness can not receive region and environmental limit, thereby can satisfy the urgent need of " peak load shifting " of all kinds of electric power systems.Multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons among the present invention can be realized the reversible hydrogen that stores in 50 to 280 ℃ temperature range, hydrogen storage capability can reach 8.0wt%.
We think that fuel cell can realize by following electrochemical reaction:
Aromatic rings hydrogenation molecule+O
2→ aromatic rings molecule+H
2O (1)
The principle of above-mentioned discharge dehydrogenation reaction (1) is as shown in Figure 1; Aromatic rings hydrogenation molecule directly generates aromatic rings molecule and proton in the anode generation incomplete oxidation dehydrogenation discharge of battery; Wherein proton through electrolyte diffusion to negative electrode, on negative electrode with the oxygen generation water that reacts.The Hydrogen Energy that directly will be stored in the hydrogenated aromatic toroidal molecule has thus changed into electric energy, and without the process of release hydrogen.Its product is mainly aromatic rings molecule and water, and fragrance changes molecule can carry out hydrogenation again again.Aromatic rings molecule and hydrogenation molecule thereof have played hydrogen storage material respectively and the effect of hydrogen source directly are provided.The battery that reaction (1) that hence one can see that is constituted is the direct fuel cell of hydrogenation hydrogen storage material capable of circulation.For being called the direct fuel cell of R-(the direct fuel cell of Reversible-) for simplicity, to be different from existing organic substance by the direct fuel cell of complete oxidation.
Principle of the present invention:
The direct fuel cell of R-is a novel direct fuel cell, and its principle is as shown in Figure 1, and cell reaction is: hydrogen storage material hydride molecule+O
2→ hydrogen storage material molecule+H
2O.The cell apparatus structure is as shown in Figure 2; When operation of fuel cells; Hydrogen storage material hydride in the hydrogen storage material hydride jar (storage tank is separated into hydrogen storage material jar and hydrogen storage material hydride jar by active clapboard) is pumped to galvanic anode and directly anode generation dehydrogenation exoelectrical reaction, generates hydrogen storage material molecule and proton, and the hydrogen storage material molecule flows out electrode and gets into the hydrogen storage material jar; And proton through electrolyte diffusion to negative electrode, on negative electrode with the oxygen generation water that reacts.This system can adopt the membrane electrode mode to constitute pile.Each monomer in the pile comprises flow-field plate, seal, membrane electrode (as shown in Figure 4).
The invention has the beneficial effects as follows: owing to do not need first release hydrogen, not only simplified device, also significantly improved fail safe, this direct fuel cell has characteristic of simple structure.Simultaneously,, conveniently adjust monocell use number in the battery pile at any time, change the power output of battery, to adapt to the electric automobile needs of speed change at random because the direct fuel of R-is in the automatic dehydrogenation of the Shi Buhui that opens circuit at external circuit and causes waste.The direct fuel cell of above R-can directly apply to the mobile traffic field, as vehicle-mounted power, compared to existing vehicle-mounted fuel cell system.
Description of drawings
Fig. 1 is direct fuel cell schematic diagram.
Fig. 2 is the direct fuel cell structure figure of R-.
Fig. 3 is a structural representation of the present invention.
Fig. 4 is the electric pile structure sketch map.
Fig. 5 is a flow of liquid field plate left view.
Reference numeral: 1-gas stream field plate, 2-seal, 3-membrane electrode; 9-flow of liquid field plate, 10-air flow channel, 11-air and water flow passage; The 12-flow channel for liquids, 13-hydrogen storage material hydride input port, the outlet of 14-hydrogen storage material; The 15-air cooling unit, 16-hydrogen storage material efferent duct, 17-hydrogen storage material jar; 18-hydrogen storage material hydride jar, 19-hydrogen storage material hydride pump, 20-hydrogen storage material hydride input pipe, 21-air inlet, 22-water pot, 23-gas outlet, 24-outlet pipe, 25-delivery port, 26-fuel cell.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
As shown in Figure 3, a kind of direct fuel cell based on the organic liquid hydrogen storage material, it comprises fuel cell 26, fuel cell 26 links to each other with load through the AC/DC change-over circuit; Hydrogen storage material on the fuel cell 26 outlet 14 is connected with hydrogen storage material jar 17 by hydrogen storage material efferent duct 16; Hydrogen storage material hydride input port 13 on the fuel cell 26 is connected with hydrogen storage material hydride jar 18 by hydrogen storage material hydride input pipe 20, and hydrogen storage material hydride input pipe 20 is provided with hydrogen storage material hydride pump 19; Delivery port 25 on the fuel cell 26 is connected with water pot 22 by outlet pipe 24, the air inlet 21 on the fuel cell 26 with advance oxygen hose and be connected; Gas outlet 23 is arranged at water pot 22 tops; Fill hydrogen storage material in the hydrogen storage material jar 17, said hydrogen storage material is a multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons, and multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons is specially the quinoline hydrogen storage material, and its hydrogen storage capability is 6.2wt%.
Direct fuel cell based on the organic liquid hydrogen storage material; As shown in Figure 3; Be formed by stacking (structure of fuel cell 26 is existing structure) successively fuel cell 26; Each fuel cell structure is identical, includes gas stream field plate 1, flow of liquid field plate 9, membrane electrode 3 and seal 2.Hydrogen storage material outlet 14 and hydrogen storage material hydride input port 13 are arranged on the fuel cell 26, have air and water flow passage 11 on the gas stream field plate 1, flow channel for liquids 12 (like Fig. 4, shown in Figure 5) is arranged on the flow of liquid field plate 9.
Embodiment 2:
Basic identical with embodiment 1; Difference is: said multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons is specially the binary mixed hydrogen storage materials of quinoline, N-ethyl carbazole; The mass ratio of two kinds of components is a quinoline: N-ethyl carbazole=5: 3, its hydrogen storage capability are 5.2wt%.
Embodiment 3:
Basic identical with embodiment 1; Difference is: said multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons is specially the ternary mixed hydrogen storage materials of N-methyl carbazole, quinoline and N-ethyl carbazole; The mass ratio of three kinds of components is a N-methyl carbazole: quinoline: N-ethyl carbazole=1: 4: 3, its hydrogen storage capability are 5.7wt%.
Embodiment 4:
Basic identical with embodiment 1; Difference is: said multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons is specially the quaternary mixed hydrogen storage materials of carbazole, N-methyl carbazole, N-ethyl carbazole and quinoline; The mass ratio of four kinds of components is a carbazole: N-methyl carbazole: N-ethyl carbazole: quinoline=1: 2: 4: 1, and its hydrogen storage capability is 5.8wt%.
Embodiment 5:
Basic identical with embodiment 1; Difference is: said multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons is specially the quaternary mixed hydrogen storage materials of carbazole, N-methyl carbazole, N-ethyl carbazole and quinoline; The mass ratio of four kinds of components is a carbazole: N-methyl carbazole: N-ethyl carbazole: quinoline=2: 1: 3: 5, and its hydrogen storage capability is 5.4wt%.
Each raw material of the multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons that the present invention is cited can both be realized the present invention, does not enumerate embodiment one by one at this.
Claims (5)
1. direct fuel cell based on the organic liquid hydrogen storage material, it comprises fuel cell (26), fuel cell (26) links to each other with load through the AC/DC change-over circuit; It is characterized in that: the hydrogen storage material outlet (14) on the fuel cell (26) is connected with hydrogen storage material jar (17) by hydrogen storage material efferent duct (16); Hydrogen storage material hydride input port (13) on the fuel cell (26) is connected with hydrogen storage material hydride jar (18) by hydrogen storage material hydride input pipe (20), and hydrogen storage material hydride input pipe (20) is provided with hydrogen storage material hydride pump (19); Delivery port (25) on the fuel cell (26) is connected with water pot (22) by outlet pipe (24), the air inlet (21) on the fuel cell (26) with advance oxygen hose and be connected; Gas outlet (23) is arranged at water pot (22) top; The hydrogen storage material jar fills hydrogen storage material in (17), and said hydrogen storage material is a multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons.
2. a kind of direct fuel cell according to claim 1 based on the organic liquid hydrogen storage material; It is characterized in that: described multi-kinds mixtures liquid attitude unsaturated heterocycle aromatic hydrocarbons is specially any one or any mixing more than two kinds in a plurality of liquid unsaturated heterocycle aromatic hydrocarbon molecules, and any is any proportioning when mixing more than two kinds.
3. a kind of direct fuel cell according to claim 2 based on the organic liquid hydrogen storage material; It is characterized in that: the heterocycle in the described liquid unsaturated heterocycle aromatic hydrocarbon molecule can be that all rings are heterocycle; Also part heterocycle, hetero-atom total quantity scope is 1 to 20; Heterocycle and aromatic ring total quantity are 1 to 20; The carbon atom number is 4 to 10 in the single ring in the liquid unsaturated heterocycle aromatic hydrocarbon molecule.
4. a kind of direct fuel cell based on the organic liquid hydrogen storage material according to claim 3 is characterized in that: the hetero-atom in the heterocycle be in nitrogen, oxygen, the sulphur any one or any more than two kinds.
5. a kind of direct fuel cell based on the organic liquid hydrogen storage material according to claim 2 is characterized in that: liquid unsaturated heterocycle aromatic hydrocarbon molecule is carbazole, N-methyl carbazole, N-ethyl carbazole, indoles or quinoline.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101391738A CN102800880A (en) | 2011-05-27 | 2011-05-27 | Direct fuel cell based on organic liquid hydrogen storage material |
| KR1020137030454A KR20140016966A (en) | 2011-05-27 | 2012-05-17 | Hydrogen storage liquid organic material-based direct fuel cell and system for energy storage and energy supply |
| PCT/CN2012/075628 WO2012163227A1 (en) | 2011-05-27 | 2012-05-17 | Hydrogen storage liquid organic material-based direct fuel cell and system for energy storage and energy supply |
| JP2014511718A JP5759620B2 (en) | 2011-05-27 | 2012-05-17 | Direct fuel cell and energy storage and supply system using organic liquid phase hydrogen storage material |
| EP12792765.5A EP2717372A4 (en) | 2011-05-27 | 2012-05-17 | Hydrogen storage liquid organic material-based direct fuel cell and system for energy storage and energy supply |
| US14/086,242 US20140080026A1 (en) | 2011-05-27 | 2013-11-21 | Energy storage and supply system and direct fuel cell based on organic liquid hydrogen storage materials |
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|---|---|---|---|
| CN2011101391738A CN102800880A (en) | 2011-05-27 | 2011-05-27 | Direct fuel cell based on organic liquid hydrogen storage material |
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| CN102800880A true CN102800880A (en) | 2012-11-28 |
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Cited By (7)
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| CN108105583A (en) * | 2018-03-06 | 2018-06-01 | 栾福超 | A kind of new compound stores hydrogen storage equipment |
| CN108386706A (en) * | 2018-03-06 | 2018-08-10 | 栾福超 | A kind of modified compound storage hydrogen storage equipment |
| CN109707529A (en) * | 2017-10-26 | 2019-05-03 | 云南电网有限责任公司电力科学研究院 | A kind of hydrogen-feeding system and thermomotor integral system |
| CN109704275A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Organic liquid hydrogen storage system and hydrogen storage method |
| CN110820008A (en) * | 2019-11-27 | 2020-02-21 | 云南电网有限责任公司电力科学研究院 | Water electrolytic cell for absorbing hydrogen by organic liquid |
| CN112331881A (en) * | 2020-10-19 | 2021-02-05 | 北京科技大学 | Modularized air cooling heat dissipation plate suitable for air cooling type proton exchange membrane fuel cell |
| CN117117225A (en) * | 2023-10-24 | 2023-11-24 | 陕西氢易能源科技有限公司 | Direct organic liquid fuel cell based on liquid hydrogen storage material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109707529A (en) * | 2017-10-26 | 2019-05-03 | 云南电网有限责任公司电力科学研究院 | A kind of hydrogen-feeding system and thermomotor integral system |
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| CN109704275B (en) * | 2017-10-26 | 2021-08-03 | 中国石油化工股份有限公司 | Organic liquid hydrogen storage system and hydrogen storage method |
| CN108105583A (en) * | 2018-03-06 | 2018-06-01 | 栾福超 | A kind of new compound stores hydrogen storage equipment |
| CN108386706A (en) * | 2018-03-06 | 2018-08-10 | 栾福超 | A kind of modified compound storage hydrogen storage equipment |
| CN110820008A (en) * | 2019-11-27 | 2020-02-21 | 云南电网有限责任公司电力科学研究院 | Water electrolytic cell for absorbing hydrogen by organic liquid |
| CN112331881A (en) * | 2020-10-19 | 2021-02-05 | 北京科技大学 | Modularized air cooling heat dissipation plate suitable for air cooling type proton exchange membrane fuel cell |
| CN117117225A (en) * | 2023-10-24 | 2023-11-24 | 陕西氢易能源科技有限公司 | Direct organic liquid fuel cell based on liquid hydrogen storage material |
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Application publication date: 20121128 |