CN103151577A - 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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- CN103151577A CN103151577A CN2012105625679A CN201210562567A CN103151577A CN 103151577 A CN103151577 A CN 103151577A CN 2012105625679 A CN2012105625679 A CN 2012105625679A CN 201210562567 A CN201210562567 A CN 201210562567A CN 103151577 A CN103151577 A CN 103151577A
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- hydrogen oxygen
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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 is that a kind of employing metal (as magnesium, aluminium, zinc etc.) is anode fuel, and in air, oxygen is as oxidant, and alkali lye or neutral brine are as the electrochemical reaction appts of electrolyte solution.The metal reserves such as China's magnesium, aluminium, zinc are abundant and cheap, so 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 characteristics such as product is pollution-free, work is quiet.Take magnesium/air cell as example, its theoretical energy density is up to 3910Wh/kg.Magnesium/air cell electrode reaction and battery overall reaction are respectively,
Anode electrode reaction: Mg-2OH
-→ Mg (OH)
2-2e
--2.69V (1)
Cathode electrode reaction: 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)
In the time of magnesium/air cell anode generation magnesia reaction, also follow 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 reduced 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, take at present to such an extent that method mainly comprises: (1) improves the magnesium alloy overpotential of hydrogen evolution by adding the high metal (as Sn, In etc.) of overpotential of hydrogen evolution in the anode metal; (2) adding hydrogen inhibitor (as stannate, thiocarbamide etc.) in electrolyte slows down hydrogen and separates out.But said method is not only limited to the evolving hydrogen reaction inhibitory action, also can reduce the performance of metal-air batteries simultaneously; (3) people's such as Gu Xiaoqing Chinese invention patent " double-fuel cell " (publication number CN 1434538A) proposes to adopt hydrogen oxygen fuel cell to eliminate metal-air batteries anodic attack accessory substance hydrogen, consists of " double-fuel cell " with metal-air batteries.Should connect by a gas piping between " double-fuel cell ", and the integrated structure of two kinds of batteries do not carried out rational layout, and be only the simple combination of two kinds of independent batteries.There are the problems such as complex structure, working service inconvenience in this technical scheme, has limited its actual property.In patent (application number 200810228230.8), metal aeration cell and hydrogen oxygen fuel cell are formed the integral type integrated drive generator, realized the original position utilization of hydrogen.Yet this structure exists in actual use that hydrogen utilization ratio is low, hydrogen oxygen fuel cell anode collector material is perishable, easily by shortcomings such as product coverings, stability is lower for anode catalyst.Therefore, developing more efficient, stable hydrogen utilization technology is the effective way that solves metal-air batteries anode liberation of hydrogen problem, also becomes the key that metal-air batteries research and through engineering approaches are used.
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 that adopts hydrogen oxygen fuel cell to realize anode liberation of hydrogen recycling.Hydrogen oxygen fuel cell is integrated in metal-air batteries top, and the hydrogen that during the metal-air batteries discharge, anode is separated out is supplied with hydrogen oxygen fuel cell on top cover as anode fuel, generates electricity by hydrogen oxygen fuel cell, and the chemical energy of hydrogen is converted into electric energy.The method has been simplified the structure of metal-air batteries and hydrogen oxygen fuel cell on the one hand; The hydrogen of on the other hand, the metal-air batteries anode being separated out is forced to have improved the utilance of hydrogen in the diffusion of hydrogen oxygen fuel cell anode-side 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 metal-air batteries module top, in described metal-air batteries module top, with hydrogen oxygen fuel cell module contact-making surface on offer the hydrogen stream port; The 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 superimposed successively anode, film, negative electrode, and described hydrophobic breathable layer amplexiforms mutually with anode in membrane electrode; Described membrane electrode anode-side down, be placed horizontally at hydrophobic breathable layer top, hydrophobic, air-permeability is placed on metal-air batteries module top, and described hydrogen stream port is connected with described hydrophobic breathable layer;
Described hydrogen oxygen fuel cell module top is provided with and the vertical hydrogen outlet that communicates of 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 outlet 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 the PTFE film or be coated with the PVDF film;
In the porous ceramic of the porous carbon fiber of PTFE dipping or PTFE dipping, the content of PTFE is 40-80wt%.
Described metal-air cell module is comprised of the cell more than or two, and wherein the electrolyte cavities top of each cell all is connected with described hydrogen stream port.
The short lines distance of the level of described hydrogen stream port and described hydrogen outlet is not less than the length of short sides of membrane electrode.
Described hydrophobic breathable layer area is greater than described membrane electrode area.
On described metal-air batteries and hydrogen oxygen fuel cell circuit, series connection or in parallel or string and series-parallel connection are connected.
Compared with prior art, the present invention has the following advantages:
1. the hydrogen that produces in the time of metal-air batteries can being worked effectively utilizes, and has improved its utilization ratio, has improved simultaneously the current efficiency of this integrated drive generator;
2. reduce metal-air batteries and assembled the danger that produces because of hydrogen;
3. avoid the electrode corrosion of hydrogen oxygen fuel cell, can guarantee the long-time steady operation of hydrogen oxygen fuel cell;
4. this integrated drive generator is simple in structure, and is easy to implement.
Description of drawings
Fig. 1. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator structural representation;
1 is the metal-air batteries module; 2 is the hydrogen oxygen fuel cell module; 3 is the hydrogen stream port; 4 is hydrophobic breathable layer; 5 is the hydrogen oxygen fuel cell anode; 6 is dielectric film; 7 is the hydrogen oxygen fuel cell negative electrode; 8 is the hydrogen outlet; 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 above-mentioned test condition, magnesium/air cell-hydrogen oxygen fuel cell integrated drive generator discharge voltage can reach 0.55V, and within 3 hours continuous discharge time zero attenuation almost.This shows that this integrated drive generator structure discharges the utilance of hydrogen when obviously having improved metal-air batteries work, improved the current efficiency of whole system, and this structure do not affect by electrolyte corrosion etc. can, but long-time steady operation.
Embodiment
A kind of magnesium/air cell-hydrogen oxygen fuel cell integral type integrated drive generator.Magnesium/air cell middle-jiao yang, function of the spleen and stomach AZ61 magnesium alloy very wherein; Negative electrode comprises Catalytic Layer, hydrophobic diffusion layer and afflux negative electrode, and electrode area is 224cm
2Cathode catalysis layer carries Mn oxide as catalyst take carbon, and carrying capacity is 6mg cm
-2, 20% PTFE is hydrophober; Hydrophobic diffusion layer is the graphitized carbon fibre felt of 3cm for the thickness after processing through PTFE emulsion hydrophobisation; PTFE accounts for the 40-85% of hydrophobic diffusion layer gross mass; The afflux layer is nickel foam, and whole magnesium air cell module is composed in series by above-mentioned 1 same cell, and the 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 the Nafion212 proton exchange membrane, and anode collector is the titanium net, and electrode area is 30cm
2
Hydrogen oxygen fuel cell anode-side level down is placed in above magnesium/air cell heap, hydrogen oxygen fuel cell cathode collector plate is the porous copper mesh, air can directly arrive the hydrogen oxygen fuel cell negative electrode by the hole on copper mesh, and the hydrogen oxygen fuel cell anode-side is amplexiformed the hydrophobic breathable layer of being made by the porous carbon fiber of 60%PTFE dipping;
Magnesium/air cell is piled the top and is provided with a rectangle hydrogen stream port, electrode in the long limit of hydrogen stream port and magnesium/air cell heap is vertical, the hydrogen that guarantees each magnesium/air cell discharging can enter into by this hydrogen outlet the hydrophobic breathable layer of hydrogen oxygen fuel cell module, guarantees that the fuel of hydrogen oxygen fuel cell anode-side is supplied with relatively even.
In the 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 are as shown in Figure 2.
Claims (8)
1. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator, comprise metal-air batteries module and hydrogen oxygen fuel cell module, it is characterized in that:
Described hydrogen oxygen fuel cell module is fixed in metal-air batteries module top, in described metal-air batteries module top, with hydrogen oxygen fuel cell module contact-making surface on offer the hydrogen stream port; The 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 superimposed successively anode, film, negative electrode, and described hydrophobic breathable layer amplexiforms mutually with anode in membrane electrode; Described membrane electrode anode-side down, be placed horizontally at hydrophobic breathable layer top, hydrophobic, air-permeability is placed on metal-air batteries module top, and described hydrogen stream port is connected with described hydrophobic breathable layer;
Described hydrogen oxygen fuel cell module top is provided with and the vertical hydrogen outlet that communicates of described hydrophobic breathable layer.
2. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator as claimed in claim 1, it 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, it is characterized in that: 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%.
4. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator as claimed in claim 1 is characterized in that: described hydrogen outlet 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 the PTFE film or be coated with the PVDF film;
In the porous ceramic of the porous carbon fiber of PTFE dipping or PTFE dipping, the content of PTFE is 40-80wt%.
5. 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 cell module is comprised of the cell more than or two, and wherein the electrolyte cavities top of each cell all is connected with described hydrogen stream port.
6. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator as claimed in claim 1 is characterized in that: the short lines distance of the level of described hydrogen stream port and described hydrogen outlet is not less than the length of short sides of membrane electrode.
7. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator as claimed in claim 1, it is characterized in that: described hydrophobic breathable layer area is greater than described membrane electrode area.
8. metal-air batteries-hydrogen oxygen fuel cell integral type integrated drive generator as claimed in claim 1 is characterized in that: on described metal-air batteries and hydrogen oxygen fuel cell circuit, series connection or in parallel or string and series-parallel connection are 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 CN103151577B (en) | 2015-07-22 |
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Cited By (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 |
| CN107431222A (en) * | 2014-12-22 | 2017-12-01 | 智能能源有限公司 | Anode chamber with variable volume |
| CN108183287A (en) * | 2016-12-08 | 2018-06-19 | 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 |
| CN110571445A (en) * | 2019-09-27 | 2019-12-13 | 张德镇 | metal fuel hydrogen power generation device |
| CN113690478A (en) * | 2021-07-15 | 2021-11-23 | 徐州科华能源科技有限公司 | Integrated power generation system based on aluminum-air battery and hydrogen fuel cell |
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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 |
Cited By (7)
| 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 |
| CN107431222A (en) * | 2014-12-22 | 2017-12-01 | 智能能源有限公司 | Anode chamber with variable volume |
| CN108183287A (en) * | 2016-12-08 | 2018-06-19 | 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 |
| CN110571445A (en) * | 2019-09-27 | 2019-12-13 | 张德镇 | metal fuel hydrogen power generation device |
| CN113690478A (en) * | 2021-07-15 | 2021-11-23 | 徐州科华能源科技有限公司 | Integrated power generation system based on aluminum-air battery and hydrogen fuel cell |
| 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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| CN103151577B (en) | 2015-07-22 |
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