CN103151577B - Metal/air battery-hydrogen oxygen fuel cell integration type combination power supply - Google Patents
Metal/air battery-hydrogen oxygen fuel cell integration type combination power supply Download PDFInfo
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- CN103151577B CN103151577B CN201210562567.9A CN201210562567A CN103151577B CN 103151577 B CN103151577 B CN 103151577B CN 201210562567 A CN201210562567 A CN 201210562567A CN 103151577 B CN103151577 B CN 103151577B
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- fuel cell
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Abstract
Provided is a metal/air battery-hydrogen oxygen fuel cell integration type combination power supply. The metal/air battery-hydrogen oxygen fuel cell integration type combination power supply comprises a metal/air battery module and a hydrogen oxygen fuel cell module, wherein the hydrogen oxygen fuel cell module is fixedly connected with the upper position of the metal/air battery module, and a hydrogen circulation opening is formed in a contact surface between the hydrogen oxygen fuel cell module and the top portion of the metal/air battery module; the hydrogen oxygen fuel cell module comprises a hydrophobic ventilating layer and membrane electrodes, the hydrophobic ventilating layer is attached to the positive electrode of the membrane electrodes; the positive electrode of the membrane electrodes is downward, and vertically arranged in the hydrogen oxygen fuel cell module, and the hydrogen circulation opening is communicated with the hydrophobic ventilating layer; and a hydrogen discharging opening which is vertically communicated with the hydrophobic ventilating layer is arranged on the top portion of the hydrogen oxygen fuel cell module. The metal/air battery-hydrogen oxygen fuel cell integration type combination power supply achieves recycle of the hydrogen in the metal/air battery, improves using efficiency of the hydrogen, lowers danger caused by accumulating the hydrogen, and improves current efficiency of the metal/air battery-hydrogen oxygen fuel cell integration type combination power supply simultaneously. In the meantime, the metal/air battery-hydrogen oxygen fuel cell integration type combination power supply has the advantages of being simple in structure, easy to achieve and the like.
Description
Technical field
The present invention relates to metal-air batteries, specifically a kind of for metal-air batteries anode liberation of hydrogen reutilization technologies such as magnesium, aluminium, zinc;
The present invention relates to metal-air batteries and hydrogen oxygen fuel cell integrated drive generator field.
Background technology
Metal-air batteries a kind of adopts metal (as magnesium, aluminium, zinc etc.) to be anode fuel, and in air, oxygen is as oxidant, and alkali lye or neutral brine are as the electrochemical reaction appts of electrolyte solution.Metal rich reserves such as China's magnesium, aluminium, zinc and cheap, therefore metal-air batteries has broad application prospects at numerous areas such as movable power source such as China's communication power supply, field emergency power supply, mains lighting supply and redundant electrical powers.Metal-air batteries has that energy density is high, reactant and the feature such as product is pollution-free, work is quiet.For magnesium/air cell, its theoretical energy density is up to 3910Wh/kg.Magnesium/air cell electrode reaction and battery overall reaction are respectively,
Anode electrode reacts: Mg-2OH
-→ Mg (OH)
2-2e
--2.69V (1)
Cathode electrode reacts: 1/2O
2-H
2o-2e
-→ 2OH
-+ 0.4V (2)
Battery overall reaction: Mg-1/2O
2-H
2o → Mg (OH)
2+ 3.09V (3)
While magnesium/air cell anode generation magnesium oxidation reaction, also with the carrying out of liberation of hydrogen side reaction, its reaction equation as the formula (4).
Evolving hydrogen reaction: Mg+2H
2o → Mg (OH)
2+ H
2↑ (4)
The carrying out of metal-air batteries anode evolving hydrogen reaction not only reduces utilance and the anodic current efficiency of metal, and the hydrogen that reaction produces also will bring certain potential safety hazard.Therefore, anodic attack liberation of hydrogen problem has become one of allowed important technical challenges in the practical process of metal-air batteries.For metal-air batteries anode liberation of hydrogen problem, adopt adquisitiones at present and mainly comprise: (1) improves magnesium alloy overpotential of hydrogen evolution by adding the high metal of overpotential of hydrogen evolution (as Sn, In etc.) in anode metal; (2) add hydrogen inhibitor (as stannate, thiocarbamide etc.) in the electrolytic solution and slow down hydrogen precipitation.But said method is not only limited to evolving hydrogen reaction inhibitory action, also can reduce the performance of metal-air batteries simultaneously; (3) Chinese invention patent " double-fuel cell " (publication number CN 1434538A) of the people such as Gu Xiaoqing proposes to adopt hydrogen oxygen fuel cell to eliminate metal-air batteries anodic attack byproduct hydrogen gas, forms " double-fuel cell " with metal-air batteries.Should be connected by a gas piping between " double-fuel cell ", and rational layout not carried out to the integrated structure of two kinds of batteries, and be only the simple combination of two kinds of independent batteries.There is the problem such as complex structure, working service inconvenience in this technical scheme, limits its actual property.In patent (application number 200810228230.8), metal aeration cell and hydrogen oxygen fuel cell are formed integral type integrated drive generator, the original position achieving hydrogen utilizes.But this structure exists that hydrogen utilization ratio is low, hydrogen oxygen fuel cell anode collector material is perishable in actual use, anode catalyst easily by shortcomings such as product coverings, stability is lower.Therefore, developing more efficient, stable hydrogen utilization technology is the effective way solving metal-air batteries anode liberation of hydrogen problem, also becomes the key of metal-air batteries research and through engineering approaches application.
Summary of the invention
The present invention is directed to the problem of existing metal-air batteries anode liberation of hydrogen, propose a kind of method adopting hydrogen oxygen fuel cell to realize anode liberation of hydrogen recycling.Be integrated in by hydrogen oxygen fuel cell above metal-air batteries, the hydrogen oxygen fuel cell on the hydrogen supply top cover that during metal-air batteries electric discharge, anode is separated out is as anode fuel, and being generated electricity by hydrogen oxygen fuel cell, is electric energy by the chemical energy of hydrogen.The method simplifies the structure of metal-air batteries and hydrogen oxygen fuel cell on the one hand; On the other hand, the hydrogen of being separated out by metal-air batteries anode is forced, in the diffusion of hydrogen oxygen fuel cell anode-side, to improve the utilance of hydrogen by porous channel.
For achieving the above object, the present invention adopts following concrete scheme to realize:
A kind of metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator, comprise metal-air batteries module and hydrogen oxygen fuel cell module, described hydrogen oxygen fuel cell module is fixed in above metal-air batteries module, in described metal-air batteries module top, with hydrogen oxygen fuel cell module contact face on offer hydrogen stream port; Hydrogen stream port is connected with the anode chamber of metal-air batteries module;
Described hydrogen oxygen fuel cell module comprises hydrophobic breathable layer and membrane electrode, and membrane electrode comprises anode superimposed successively, film, negative electrode, and described hydrophobic breathable layer amplexiforms mutually with the anode in membrane electrode; Described membrane electrode anode-side down, be placed horizontally at above hydrophobic breathable layer, hydrophobic, air-permeability is placed on above metal-air batteries module, and described hydrogen stream port is connected with described hydrophobic breathable layer;
Described hydrogen oxygen fuel cell module top is provided with the hydrogen discharge that communicate vertical with described hydrophobic breathable layer.
Hydrogen oxygen fuel cell in described hydrogen oxygen fuel cell module is air-breathing formula hydrogen oxygen fuel cell.
Described hydrophobic breathable layer is the porous carbon fiber of PTFE dipping or the porous ceramic of PTFE dipping, and wherein the content of PTFE is 40-80wt%.
Described hydrogen discharge or be filled with PTFE dipping porous carbon fiber be filled with PTFE dipping porous ceramic or be coated with PTFE film or be coated with PVDF thin film;
In the porous ceramic that the porous carbon fiber of PTFE dipping or PTFE flood, the content of PTFE is 40-80wt%.
Described metal-air cell module is made up of the cell of more than or two, and wherein the electrolyte cavities top of each cell is all connected with described hydrogen stream port.
The most short lines distance of level of described hydrogen stream port and described hydrogen discharge is not less than the length of short sides of membrane electrode.
Described hydrophobic breathable layer area is greater than described membrane electrode area.
Described metal-air batteries with hydrogen oxygen fuel cell circuit to be connected or in parallel or go here and there also series-parallel connection and be connected.
Compared with prior art, the present invention has the following advantages:
1. the hydrogen produced when metal-air batteries can be worked effectively utilizes, and improves its utilization ratio, improves the current efficiency of this integrated drive generator simultaneously;
2. reduce the danger that metal-air batteries produces because of hydrogen gathering;
3. avoid the electrode corrosion of hydrogen oxygen fuel cell, the work of hydrogen oxygen fuel cell long-time stable can be ensured;
4. this integrated drive generator structure is simple, easy to implement.
Accompanying drawing explanation
Fig. 1. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator structural representation;
1 is metal-air batteries module; 2 is hydrogen oxygen fuel cell module; 3 is hydrogen stream port; 4 is hydrophobic breathable layer; 5 is hydrogen oxygen fuel cell anode; 6 is dielectric film; 7 is hydrogen oxygen fuel cell negative electrode; 8 is hydrogen discharge; 9 is hydrogen; 10 is air.
Fig. 2. magnesium/air cell-hydrogen oxygen fuel cell integral type integrated drive generator constant current discharge curve;
Magnesium/air cell constant current discharge electric current is 25 milliamperes/square centimeter, and hydrogen oxygen fuel cell constant current discharge electric current is 50 milliamperes/square centimeter.
As can be seen from the figure, under the test conditions above, magnesium/air cell-hydrogen oxygen fuel cell integrated drive generator discharge voltage can reach 0.55V, and in 3 hours continuous discharging time almost zero attenuation.This shows that this integrated drive generator structure discharges the utilance of hydrogen when significantly improving metal-air batteries work, improve the current efficiency of whole system, and this structure can not affect by electrolyte corrosion etc., can long-time steady operation.
Embodiment
A kind of magnesium/air cell-hydrogen oxygen fuel cell integral type integrated drive generator.Wherein magnesium/air cell middle-jiao yang, function of the spleen and stomach very AZ61 magnesium alloy; Negative electrode comprises Catalytic Layer, hydrophobic diffusion layer and afflux negative electrode, and electrode area is 224cm
2.Cathode catalysis layer carries Mn oxide for catalyst with carbon, and carrying capacity is 6mg cm
-2, the PTFE of 20% is hydrophober; The graphitized carbon fibre felt of hydrophobic diffusion layer to be thickness after the process of PTFE emulsion hydrophobisation be 3cm; PTFE accounts for the 40-85% of hydrophobic diffusion layer gross mass; Current collector layer is nickel foam, and whole magnesium air cell module is composed in series by above-mentioned 1 cell equally, and cell die opening is 3mm.
Hydrogen oxygen fuel cell is Proton Exchange Membrane Fuel Cells, and anode, cathod catalyst are 60%Pt/C, and carrying capacity is respectively 0.2mg cm
-2with 0.3mg cm
-2, dielectric film is Nafion212 proton exchange membrane, and anode collector is titanium net, and electrode area is 30cm
2.
Hydrogen oxygen fuel cell anode-side down level is placed in magnesium/air cell heap top, hydrogen oxygen fuel cell cathode collector plate is porous copper mesh, air directly arrives hydrogen oxygen fuel cell negative electrode by the hole on copper mesh, and hydrogen oxygen fuel cell anode-side amplexiforms the hydrophobic breathable layer that the porous carbon fiber that flooded by 60%PTFE is made;
Magnesium/air cell heap top is provided with a rectangle hydrogen stream port, the long limit of hydrogen stream port and magnesium/air cell pile in electrode vertical, ensure that the hydrogen of each magnesium/air cell discharge can enter into the hydrophobic breathable layer of hydrogen oxygen fuel cell module by this hydrogen discharge, ensure that the fuel supply of hydrogen oxygen fuel cell anode-side is relatively uniform.
In battery testing process, magnesium/air cell is at 25mA/cm
2constant current discharge, hydrogen oxygen fuel cell is at 50mA/cm
2constant current discharge, discharge curve as shown in Figure 2.
Claims (5)
1. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator, comprises metal-air batteries module and hydrogen oxygen fuel cell module, it is characterized in that:
Described hydrogen oxygen fuel cell module is fixed in above metal-air batteries module, in described metal-air batteries module top, with hydrogen oxygen fuel cell module contact face on offer hydrogen stream port; Hydrogen stream port is connected with the anode chamber of metal-air batteries module;
Described hydrogen oxygen fuel cell module comprises hydrophobic breathable layer and membrane electrode, and membrane electrode comprises anode superimposed successively, film, negative electrode, and described hydrophobic breathable layer amplexiforms mutually with the anode in membrane electrode; Described membrane electrode anode-side down, be placed horizontally at above hydrophobic breathable layer, hydrophobic, air-permeability is placed on above metal-air batteries module, and described hydrogen stream port is connected with described hydrophobic breathable layer;
Described hydrogen oxygen fuel cell module top is provided with the hydrogen discharge that communicate vertical with described hydrophobic breathable layer;
The most short lines distance of level of described hydrogen stream port and described hydrogen discharge is not less than the length of short sides of membrane electrode;
Described hydrophobic breathable layer area is greater than described membrane electrode area;
Described hydrophobic breathable layer is the porous carbon fiber of PTFE dipping or the porous ceramic of PTFE dipping, and wherein the content of PTFE is 40-80wt%.
2. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator as claimed in claim 1, is characterized in that: the hydrogen oxygen fuel cell in described hydrogen oxygen fuel cell module is air-breathing formula hydrogen oxygen fuel cell.
3. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator as claimed in claim 1, is characterized in that: described hydrogen discharge or be filled with the porous carbon fiber of PTFE dipping or be filled with the porous ceramic of PTFE dipping or be coated with PTFE film or be coated with PVDF thin film;
In the porous ceramic that the porous carbon fiber of PTFE dipping or PTFE flood, the content of PTFE is 40-80wt%.
4. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator as claimed in claim 1, it is characterized in that: described metal-air batteries module is made up of the cell of more than or two, wherein the electrolyte cavities top of each cell is all connected with described hydrogen stream port.
5. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator as claimed in claim 1, is characterized in that: described metal-air batteries with hydrogen oxygen fuel cell circuit to be connected or in parallel or go here and there also series-parallel connection and be connected.
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|---|---|---|---|
| CN201210562567.9A CN103151577B (en) | 2012-12-21 | 2012-12-21 | Metal/air battery-hydrogen oxygen fuel cell integration type combination power supply |
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| CN201210562567.9A CN103151577B (en) | 2012-12-21 | 2012-12-21 | Metal/air battery-hydrogen oxygen fuel cell integration type combination power supply |
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| CN103151577B true CN103151577B (en) | 2015-07-22 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101747506B1 (en) * | 2014-12-22 | 2017-06-15 | 주식회사 포스코아이씨티 | Secondary Battery System and Method for Charging/Discharging Secondary Battery System |
| US9954235B2 (en) * | 2014-12-22 | 2018-04-24 | Intelligent Energy Limited | Anode chambers with variable volumes |
| CN108183287B (en) * | 2016-12-08 | 2019-09-06 | 中国科学院大连化学物理研究所 | Metal fuel cell system with hydrogen elimination function |
| CN108546146A (en) * | 2018-04-10 | 2018-09-18 | 云南铝业股份有限公司 | Metal fuel battery waterproof ventilative layer and preparation method thereof |
| CN110571445B (en) * | 2019-09-27 | 2023-01-24 | 张德镇 | Metal fuel hydrogen power generation device |
| CN113690478B (en) * | 2021-07-15 | 2022-10-25 | 徐州科华能源科技有限公司 | Integrated power generation system based on aluminum-air battery and hydrogen fuel battery |
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|---|---|---|---|---|
| CN1434538A (en) * | 2002-01-24 | 2003-08-06 | 顾晓青 | Double-fuel cell |
| CN101159333A (en) * | 2007-09-28 | 2008-04-09 | 哈尔滨工业大学 | Self-respiration type fuel battery membrane electrode and method for producing the same |
| CN101728598A (en) * | 2008-10-22 | 2010-06-09 | 中国科学院大连化学物理研究所 | Integrated combined power supply of metal oxygen cell/hydrogen-oxygen fuel cell |
| CN102055046A (en) * | 2009-11-06 | 2011-05-11 | 天津市斗星机械设备有限公司 | Bifuel battery unit of electric vehicle |
-
2012
- 2012-12-21 CN CN201210562567.9A patent/CN103151577B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434538A (en) * | 2002-01-24 | 2003-08-06 | 顾晓青 | Double-fuel cell |
| CN101159333A (en) * | 2007-09-28 | 2008-04-09 | 哈尔滨工业大学 | Self-respiration type fuel battery membrane electrode and method for producing the same |
| CN101728598A (en) * | 2008-10-22 | 2010-06-09 | 中国科学院大连化学物理研究所 | Integrated combined power supply of metal oxygen cell/hydrogen-oxygen fuel cell |
| CN102055046A (en) * | 2009-11-06 | 2011-05-11 | 天津市斗星机械设备有限公司 | Bifuel battery unit of electric vehicle |
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