CN102468510A - Indirect methanol fuel cell device based on heteropoly compound energy storage - Google Patents
Indirect methanol fuel cell device based on heteropoly compound energy storage Download PDFInfo
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Abstract
The invention discloses an indirect methanol fuel cell device based on heteropoly compound energy storage, belonging to the field of new energy resources. In order to solve the problems of overhigh cost of an electrode catalyst of a direct methanol fuel cell, catalyst damage caused by intermediate products, mixed potential generated by methanol permeating in a cathode, reduced performance of the cell, environment pollution, and the like, the invention provides a fuel cell system in which a heteropoly compound stores methanol energy and discharge cycle is carried out on the fuel cell, an intermediate reactor is arranged in a direct methanol fuel cell system, the heteropoly compound is used for oxidizing the methanol under the action of a catalyst in the intermediate reactor, the methanol energy is stored in a reduction-state heteropoly compound in forms of protons and electrons, then the reduction-stage heteropoly compound is separated and then is conveyed to an anode of the fuel cell to be oxidized for recycling, and the recycled heteropoly compound is sent to the intermediate reactor to react with the methanol so as to be recycled. The invention is suitable for power generation of a stationary electric power plant, or other portable and distributed power supply systems.
Description
Technical field:
The invention belongs to new energy field.Relate to a kind ofly, and on fuel cell pile, carry out the fuel-cell device of discharge cycles, be applicable to stationary electric power plant generating or other portable, distributed power supply systems with heteropoly compound storing methanol energy.
Background technology:
Fuel cell power generation is the 4th a type of generation technology after waterpower, firepower and nuclear energy power generation.Because it is a kind ofly directly with the electrochemical reaction mode chemical energy of fuel to be converted into the TRT of electric energy without burning, theoretically, as long as continuous fueling, fuel cell just can uninterruptable power generation.Fuel cell has advantages such as generating efficiency height, environmental pollution are little, no matter is as central concentration type or regional decentralized power plant, and is still all most suitable as the type field power plant of factory, biotope, heavy construction crowd and mobile power device.
DMFC (Direct Methanol Fuel Cell; DMFC) have that theoretical transformation efficient is high, start-up temperature is low, simple in structure, volume is little, storage and advantage such as easy to carry, be the ideal power source of civil and military portable power supplies and electric vehicle.The DMFC theoretical efficiency is up to 96%, exceeds more than the twice than the power supplying efficiency of traditional electrical network about 32%, thereby also is regarded as the New-generation distributed energy technology of tool prospect.
But; Since methyl alcohol be on anode of fuel cell directly by catalytic oxidation, therefore need to use the electrode catalyst of noble metal (for example Pt) battery that acts as a fuel, to guarantee that methyl alcohol can have higher oxidation rate; The cost that this has just increased considerably fuel cell limits it and applies; In electrochemical oxidation process, the middle species of methanol oxidation (for example CO etc.) can make some catalyst poisonings and lose catalytic activity in addition; In addition, the most serious problem is that methyl alcohol can be penetrated into negative electrode through dielectric film from anode in DMFC, and this has not only reduced the utilance of methyl alcohol; And the methyl alcohol that is penetrated into negative electrode can be at cathode oxidation; Produce mixed potential, reduced the performance of battery, also can cause environmental pollution simultaneously.
Heteropoly compound (Heteropoly compand is called for short HPC) comprises heteropoly acid and heteropolyacid salt.Heteropoly acid (Heteropolyacid, be called for short HPA) be by hetero-atom (be central atom, like Si, P; Fe, Co, Ge etc.) and polyatom (be coordination atom, like W; Mo, V etc.) the one type of polyoxy bunch metal complex (Polyoxometalate is called for short POM) through the coordination of oxygen atom bridge is like H
3PW
12O
10And heteropolyacid salt is partly or entirely to replace H among the HPA by gegenion
+The metal complex that generates is like Cs
2.5H
0.5PW
12O
10Heteropoly compound have catalytic activity height, selectivity good, and can receive people and pay close attention to widely in advantages such as its oxidation-reduction qualities of the horizontal adjusted of atom/molecule.
With Keggin type heteropoly acid is example, and its general structure is H
n[XM
12O
10], (X=P, Si, Ge, As ..., M=Mo, W ...) wherein, H is a gegenion, X is hetero-atom (also claiming central atom), M is for joining atom (also claiming polyatom).
Powering fuel cells with CO via aqueous polyoxometalates and gold catalysts (W.B.Kim; T.Voitl; G.J.Rodriguez-Rivera, J.A.Dumesic.Science, 2004; 305:1280-1283) a civilian reported first adopts the Au catalyst that loads on the CNT and the heteropoly acid (polyoxometalate of liquid phase; POM) mix formation suspension, under catalyst action, heteropoly acid can be used as oxidant the CO oxidation is generated CO during room temperature
2, being in the heteropoly acid of going back ortho states stored in form energy simultaneously with proton and electronics, it discharges the oxidized regeneration of electronics on the anode of PEM, and the H+ proton permeability is crossed PEM and is got into negative electrode and be oxidised with air to water, thereby realizes discharge process.But need under high pressure carry out the oxidation reaction of CO in this cyclic process, increase the energy consumption of system, simultaneously having relatively high expectations system equipment.
Summary of the invention:
The present invention is intended to develop a kind of indirect methanol fuel cell device based on the heteropoly compound energy storage, solves the above-mentioned problems of DMFC.
In traditional direct methanol fuel cell system, set up intermediate reactor; It is the methanol oxidation reactor; Methyl alcohol does not directly feed the fuel cell electrode after fuel reservoir comes out; Mix mutually with catalyst granules, the POM solution of suspension but feed the methanol oxidation reactor, POM discharges CO with methanol catalytic oxidation
2Simultaneously with the methyl alcohol energy with the stored in form of proton and electronics in going back ortho states POM; Shown in reaction equation (1); The POM that then will go back ortho states separates with catalyst filtration to be transported to and discharges electronics on the anode of fuel cell and oxidizedly be able to regeneration, and proton then is penetrated into electronics that negative electrode and electrode transmit and the oxygen behind the humidification generation water that reacts through PEM.POM after the regeneration is transported in the intermediate reactor through pump and continues oxidation reaction takes place with methyl alcohol, is able to recycle.
Indirect methanol fuel cell device according to the present invention's proposition; The catalytic oxidation methanol process that mainly comprises heteropoly compound; Described heteropoly compound is polyoxometallate or multi-metal oxygen acid compounds or the mixture of the two; Promptly under the effect of catalyst, make heteropoly compound catalytic oxidation methyl alcohol, the methanol oxidation product is CO
2And H
+Proton, and coordination atom obtains electronics, the Mo atom valence state in shown in equation (1) reduces, and makes the heteropoly compound reduction, and then with the energy of methyl alcohol with the stored in form of proton and electronics in heteropoly compound.
Preferably, the present invention also comprises the electrochemical oxidation regenerative process of going back the ortho states heteropoly compound, and described electrochemical oxidation regenerative process is carried out on proton exchange film fuel cell electric piling; Promptly under the effect of electrode catalyst,, can not use noble metal catalyst (for example Pt) as electrode material because it is very easy oxidized to go back the ortho states heteropoly compound; This can reduce the cost of fuel cell significantly; Also the ortho states heteropoly compound discharges electronics on anode, and electronics arrives negative electrode through lead, load, lead, goes back proton that the ortho states heteropoly compound stored and sees through PEM and also reach negative electrode; With the air mixed behind above-mentioned electronics, the humidification; The generation water that reacts is accomplished the chemical oxidation of gold of discharge, goes back the ortho states heteropoly compound after the oxidation and obtains regeneration.
CH
3OH+H
2O+3PMo
12O
10 3-→CO
2+6H
++3PMo
12O
10 5- (1)
Description of drawings:
Fig. 1 is the indirect methanol fuel cell device sketch map based on the heteropoly compound energy storage of the present invention;
Among Fig. 1: 1. methanol solution storage tank; 2. methanol solution; 3. pump A; 4. mass flow controller; 5. thermoelectricity temperature sensor occasionally; 6. intermediate reactor; 7. integral catalyst layer; 8. pellet type catalyst; 9. blender; 10. condensing water inlet A; 11. internal exchanger; 12. condensation-water drain A; 13. needle-valve; 14. condenser; 15. condensation-water drain B; 16. condensing water inlet B; 17. internal ramp; 18. go back ortho states heteropoly acid solution; 19. electronic load; 20. anode of fuel cell; 21. fuel battery negative pole; 22. the air behind the humidification; 23. fuel cell pile; 24. PEM; 25.POM solution; 26. pump B;
Fig. 2 be under the different catalysts effect temperature to the influence of heteropoly compound oxidation methanol conversion
Embodiment:
Certain density methyl alcohol 2 solution, solvent are that water (selecting methanol concentration in this instance for use is 0.1M, but is not limited only to this) comes out after liquid delivery pump 3 is transported to intermediate reactor 6 after measuring with mass flowmenter 4 from fuel reservoir; In intermediate reactor 6, be provided with agitating device 9 and heat exchanger 11, in initial start up phase; Heat exchanger feeds hot water certain heat is provided, and makes the temperature of intermediate reactor 6 reach best working temperature, promptly between 60-90 ℃; After getting into the operation phase, heat exchanger 11 feeds condensed water, changes away the heat in the methanol oxidation reactor; Keep stationary temperature, after the methyl alcohol arrival intermediate reactor 6 through pump 3 conveyings, utilize blender 9; Methanol solution, heteropoly compound are fully mixed with the catalyst granules 8 of suspension, and catalytic oxidation takes place, it is as shown in Figure 2 that the conversion ratio of primary first-order equation takes place on different catalysts for methyl alcohol and heteropoly compound; Heteropoly compound electron gain, coordination atom valence state reduce and generate and go back ortho states, generate CO behind the methanol oxidation
2, can carry small amount of methanol secretly when gas is upwards overflowed, through the heteropoly compound after catalyst layer 7 and the anode regeneration once more with the methyl alcohol generation catalytic oxidation of carrying secretly, then again through condenser 14, CO
2In contained minute quantity methyl alcohol (or not containing methyl alcohol) and water condensation get off, discharge purer CO through needle-valve 13
2Also behind the ortho states heteropoly compound 18 process filters 17 filtration catalizer particles; This catalyst granules is homemade catalysis POM oxidation catalyst for methanol; Get into the anode 20 of fuel cell pile 23, under the effect of electrode catalyst, be generally Pt; Discharge electronics and arrive negative electrode 21, H through anode 20, load 19
+Proton then is penetrated into negative electrode through PEM 24; React with air 22, electronics behind the humidification, generate water, go back the then oxidized regeneration 25 of ortho states heteropoly compound; Be transported in the catalyst layer 7 of intermediate reactor 6 through pump 26; With methyl alcohol generation oxidation reaction, thereby accomplish circulation, reuse.
The catalyst activity component of catalysis POM oxidation methyl alcohol of the present invention is for contain Pt, Ru, Pd, Au, Ag, Ir, Rh at least, and wherein carrier is for contain SiO at least
2, Al
2O
3, porous carrier such as C, CNT, the active component mass content is 1～40%.
Pile of the present invention is commercially available DMFC pile.
According to above flow process; Employing is gone back the heteropoly compound of ortho states as energy storage vehicle; Be incorporated into and carry out oxidation reaction in the fuel cell; Bring several significant advantages like this: on the one hand because to go back the ortho states heteropoly compound as easy as rolling off a log oxidized, so electrode catalyst of fuel cell can not adopt noble metal, and this can significantly reduce the cost of fuel cell; On the other hand because the CO that electrode material is poisoned that discharges owing to the methanol oxidation reaction is fundamentally eliminated in not oxidation in fuel cell pile of methyl alcohol; There is the molecular dynamics diameter of super molecular compound will be far longer than methyl alcohol again resemble the heteropoly compound; This can significantly reduce the infiltration of methyl alcohol in PEM; Especially, when methanol conversion is 100% in the methanol oxidation reactor, then there is not the penetration problem of methyl alcohol among the PEM.In addition, methanol oxidation is reflected in the methanol oxidation reactor and carries out, and can from the methanol oxidation reactor, discharge the CO of higher degree
2, this has been avoided CO effectively
2In electrode, pile up and influence the phenomenon of catalyst utilization, also realized CO simultaneously
2Low energy consumption separate, so the present invention can fundamentally solve above-mentioned three subject matters of existing direct methanol fuel cell system.
Claims (17)
1. indirect methanol fuel cell device, it comprises following assembly:
A, fuel cell, it comprises anode and the negative electrode that is separated by PEM;
B, be positioned at the outside methanol oxidation reactor of said fuel cell; This inside reactor fills the medium that comprises catalyst and heteropoly compound and has first inlet, second inlet, first outlet and second outlet at least; Wherein first inlet is used to receive the methanol aqueous solution from the methyl alcohol storage tank; Said methanol aqueous solution reduces heteropoly compound under the effect of said inside reactor at catalyst, generate carbon dioxide and proton and go back the heteropoly compound of ortho states; Wherein first outlet is used to discharge carbon dioxide, and second outlet is used to discharge proton and the heteropoly compound of going back ortho states; Said second inlet is used to receive by the said heteropoly compound of going back ortho states and the heteropoly compound of regeneration oxidized at the anode place of fuel cell;
C, with proton with go back the feeding mechanism of ortho states heteropoly compound from the anode of second export supply of said methanol oxidation reactor to said fuel cell;
D, will heteropoly compound regeneration be back to the return mechanism of second inlet of said methanol oxidation reactor by the said heteropoly compound of going back ortho states is oxidized at the anode place of fuel cell.
2. the indirect methanol fuel cell device of claim 1; Wherein, Said anode comprises anode flow field board, anode diffusion layer and anode catalyst layer; Said negative electrode comprises cathode catalyst layer, cathode diffusion layer and cathode flow field plate, and their putting in order in fuel cell are followed successively by from the anode to the negative electrode: anode flow field board, anode diffusion layer, anode catalyst layer, PEM, cathode catalyst layer, cathode diffusion layer and cathode flow field plate.
3. the indirect methanol fuel cell device of claim 1, wherein from assembly b to go back the ortho states heteropoly compound oxidized at the catalyst layer of said anode, the catalyst layer at negative electrode is reduced behind the said PEM and pass from the proton of assembly b.
4. the indirect methanol fuel cell device of claim 2; Wherein said anode catalyst contains the black or Ru/C of Pt/C or Pt-Ru/C or Pt-Ru at least, and randomly contains in the following material one or more: osmium (Os), rhodium (Rh), iridium (Ir), tungsten dioxide (WO
2), tin (Sn), molybdenum (Mo); Said cathod catalyst contains Pt/C or Ru/C at least; Described C is an activated carbon; Said PEM is perfluorinated sulfonic acid type PEM or radiation grafting film or non-high fluorinated film or fluorine ion cross-linked polymer or phosphate polymer.
5. the indirect methanol fuel cell device of claim 1 wherein also is provided with agitating device, heat exchanger, condenser and thermocouple at said methanol oxidation inside reactor.
6. the indirect methanol fuel cell device of claim 1; Wherein before said first outlet, the integral catalyst layer is set; Said second inlet then is arranged between said integer catalyzer layer and said first outlet, is used for making the heteropoly compound of methyl alcohol of being carried secretly by carbon dioxide and the regeneration of returning through said second inlet to react at said integer catalyzer layer.
7. the indirect methanol fuel cell device of claim 1, wherein the said catalyst among the step b is a loaded catalyst, carrier is for contain SiO at least
2, Al
2O
3, C or CNT porous carrier, described C is an activated carbon, active component is Pt, Ru, Pd, Au, Ag, Ir or Rh or any two kinds or more kinds of mixtures in them.
8. the indirect methanol fuel cell device of claim 7, the weight of wherein said active component accounts for the 1-40% of said total catalyst weight.
9. the indirect methanol fuel cell device of claim 6, wherein said integral catalyst is a loaded catalyst, carrier is for contain SiO at least
2, Al
2O
3, C or CNT porous carrier, described C is an activated carbon, active component is Pt, Ru, Pd, Au, Ag, Ir or Rh or any two kinds or more kinds of mixtures in them, wherein said active component weight accounts for the 1-40% of said total catalyst weight.
10. the indirect methanol fuel cell device of claim 1, wherein said heteropoly compound are selected from heteropoly acid or heteropolyacid salt or the mixture of the two.
11. the indirect methanol fuel cell device of claim 1, wherein said first inlet and said second inlet are same inlet.
12. the indirect methanol fuel cell device of claim 1, wherein said medium is water and methanol mixture.
13. the indirect methanol fuel cell device of claim 1, it comprises that also transport and metering device are to be transported to said methanol aqueous solution metering in the said methanol oxidation reactor.
14. the indirect methanol fuel cell device of claim 1, it is operated under the gauge pressure of 0-0.5MPa.
15. the indirect methanol fuel cell device of claim 10, wherein said heteropoly acid comprises H
3PW
12O
40, H
1SiW
12O
10, H
3PMo
12O
10, H
1SiMo
12O
10, H
1GeW
12O
10, H
1GeMo
12O
10, H
5PW
11ZrO
10, H
5PW
11TiO
10, H
3PW
11ThO
10, H
3BW
12O
10, H
1CoW
12O
10, and the slaine of above-mentioned heteropoly acid.
16. one kind is the method for operation of the fuel cell of fuel with methyl alcohol indirectly, may further comprise the steps:
A. be arranged in the outside methanol oxidation reactor of fuel cell, making methanol aqueous solution under the effect of catalyst, reduce heteropoly compound, generation carbon dioxide and proton and go back the heteropoly compound of ortho states;
B. proton and the heteropoly compound of going back ortho states are supplied to the anode of fuel cell from said reactor; The said heteropoly compound of going back ortho states and the heteropoly compound that obtain regenerate oxidized at this anode place; Said proton passes the PEM between anode of fuel cell and negative electrode and arrives negative electrode, and is reduced at this negative electrode place.
17. the method for claim 16, wherein the heteropoly compound with said regeneration is back in the said methanol oxidation reactor to carry out step a again.
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| CN103730674A (en) * | 2012-12-31 | 2014-04-16 | 刘军 | Low-temperature liquid phase fuel reformer for flow batteries |
| CN105420289A (en) * | 2015-12-09 | 2016-03-23 | 清华大学 | Method for using lignocellulose as raw material to co-produce ethyl alcohol and electric energy |
| CN108499562A (en) * | 2018-03-13 | 2018-09-07 | 中国科学院长春应用化学研究所 | A kind of pallium-on-carbon that anti-carbon monoxide poisons-tungsten dioxide elctro-catalyst and preparation method thereof |
| CN114204067A (en) * | 2021-12-13 | 2022-03-18 | 上海交通大学 | Hydrogen storage solution based on heteropoly acid and portable fuel cell using the same |
| CN114438533A (en) * | 2022-03-10 | 2022-05-06 | 厦门大学 | Homogeneous-phase photocatalytic alcohol hydrogen production device based on electron coupling proton buffer medium and method thereof |
| CN117205919A (en) * | 2023-11-09 | 2023-12-12 | 潍坊学院 | Photo-thermal CO with full spectrum 2 Catalyst with catalytic hydrogenation activity and preparation method and application thereof |
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| CN103022545A (en) * | 2012-12-31 | 2013-04-03 | 刘军 | Multi-acid flow fuel battery system |
| CN103730674A (en) * | 2012-12-31 | 2014-04-16 | 刘军 | Low-temperature liquid phase fuel reformer for flow batteries |
| CN103738917A (en) * | 2012-12-31 | 2014-04-23 | 刘军 | Low-temperature liquid phase fuel reforming hydrogen generator and preparation method of high-purity hydrogen |
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| CN105420289A (en) * | 2015-12-09 | 2016-03-23 | 清华大学 | Method for using lignocellulose as raw material to co-produce ethyl alcohol and electric energy |
| CN105420289B (en) * | 2015-12-09 | 2019-02-05 | 清华大学 | A method of using lignocellulosic as raw material co-producing ethanol and electric energy |
| CN108499562A (en) * | 2018-03-13 | 2018-09-07 | 中国科学院长春应用化学研究所 | A kind of pallium-on-carbon that anti-carbon monoxide poisons-tungsten dioxide elctro-catalyst and preparation method thereof |
| CN114204067A (en) * | 2021-12-13 | 2022-03-18 | 上海交通大学 | Hydrogen storage solution based on heteropoly acid and portable fuel cell using the same |
| CN114204067B (en) * | 2021-12-13 | 2024-05-28 | 上海交通大学 | Hydrogen storage solution based on heteropolyacid and portable fuel cell using the same |
| CN114438533A (en) * | 2022-03-10 | 2022-05-06 | 厦门大学 | Homogeneous-phase photocatalytic alcohol hydrogen production device based on electron coupling proton buffer medium and method thereof |
| CN117205919A (en) * | 2023-11-09 | 2023-12-12 | 潍坊学院 | Photo-thermal CO with full spectrum 2 Catalyst with catalytic hydrogenation activity and preparation method and application thereof |
| CN117205919B (en) * | 2023-11-09 | 2024-03-05 | 潍坊学院 | Photo-thermal CO with full spectrum 2 Catalyst with catalytic hydrogenation activity and preparation method and application thereof |
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