CN102270777A - Reduction method for zinc oxide of zinc-air fuel cell - Google Patents
Reduction method for zinc oxide of zinc-air fuel cell Download PDFInfo
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- CN102270777A CN102270777A CN2010101908805A CN201010190880A CN102270777A CN 102270777 A CN102270777 A CN 102270777A CN 2010101908805 A CN2010101908805 A CN 2010101908805A CN 201010190880 A CN201010190880 A CN 201010190880A CN 102270777 A CN102270777 A CN 102270777A
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- zinc
- zinc oxide
- fuel cell
- air fuel
- reducing
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Abstract
The invention relates to a reduction method for zinc oxide of a zinc-air fuel cell. The method comprises: a recovery step, wherein the zinc oxide is recovered from the discharged zinc-air fuel cell; a reduction step, wherein the recovered zinc oxide is placed in a solar energy reaction apparatus, and is reduced to the gaseous zinc through adopting carbon monoxide as a reducing agent; a cooling step, wherein the gaseous zinc is subjected to a cooling process to form the solid zinc; and an electrode preparation step, wherein the solid zinc is provided for preparing the zinc electrode in the zinc-air fuel cell.
Description
Technical field
The present invention is about a kind of method of reducing of zinc oxide, particularly about a kind of method of reducing of zinc oxide of zinc/air fuel cell.
Background technology
Metal fuel battery is as the oxide in the battery with airborne oxygen, and use metallics as negative pole, such structure in various batteries be belong to have high-energy-density, the heavy-duty battery of long preservation and low-cost characteristic, so the research of metal fuel battery and development have been subjected to the attention of all circles.Wherein the most representative with zinc/air fuel cell again.
Please refer to shown in Figure 1ly, it is the structural representation of zinc/air fuel cell, and the primary structure of zinc/air fuel cell includes usually: an air pole plate 91 as negative electrode, a zincode plate 92 as anode and an electrolyte 93.Electrolyte 93 is between this air pole plate 91 and zincode plate 92, with conducting ion between air pole plate 91 and zincode plate 92.
The cathode reaction that this air pole plate 91 is carried out is as the formula (1):
The anode reaction that this zincode plate 92 is carried out is as the formula (2):
Zn(s)+2OH
-→ZnO+H
2O+2e
-E
0＝1.25V……..(2)
Its clean reaction as the formula (3):
E
0＝1.65V ……..(3)
The open circuit voltage of zinc/air fuel cell reality is between 1.35～1.45 volts (Volt), and the voltage of general practical operation is between 0.9～1.2 volt.
As described above, the zinc in the zinc/air fuel cell after discharging fully will form the zinc oxide precipitation.Collect at present usually the zinc oxide in the zinc/air fuel cell, and be zinc with solid carbon (C) with zinc oxide reduction, the zinc that reduction obtains just can be done further application.Under the temperature of 1200K, as the formula (4) with the reduction reaction of solid carbon reduction-oxidation zinc:
ZnO
(s)+C
(s)→Zn
(g)+CO
(g)，ΔH
1200K＝367.4kJ/mol........(4)
Yet, higher with solid carbon as the caloric receptivity Δ H1200K of reducing agent reduction-oxidation zinc, therefore need provide more energy can produce reaction, cause the hear rate of carrying out reduction reaction to increase; Again and, with this solid carbon as reducing agent, compared to the reducing agent of other liquid state and gaseous state, this solid carbon and this zinc oxide contact and mixture homogeneity lower, causing has the not shortcoming of complete reaction of solid carbon easily; Again and, because the temperature of carrying out above-mentioned reduction reaction need reach more than the 1200K, be heated to the high temperature of this 1200K at present with various fuel or combustion gas, it is many to cause the thermal source cost to improve relatively; Again and, do not set up at present the method that is used in zinc/air fuel cell again reclaimed in the circulation of the zinc oxide in the zinc/air fuel cell, therefore, be necessary the method for reducing of the zinc oxide of zinc/air fuel cell is further planned.
Summary of the invention
The present invention seeks to improve above-mentioned shortcoming,, be applied to the purpose that is fabricated to of zinc/air fuel cell with the zinc that zinc oxide reduction is obtained with the method for reducing of zinc oxide that a kind of zinc/air fuel cell is provided.
The present invention's time purpose provides a kind of method of reducing of zinc oxide of zinc/air fuel cell, to reduce the required hear rate energy of reduction reaction.
Still a further object of the present invention provides a kind of method of reducing of zinc oxide of zinc/air fuel cell, to reduce the thermal source cost of integrated artistic.
Method of reducing according to the zinc oxide of zinc/air fuel cell of the present invention comprises: a recycling step, by reclaiming zinc oxide in the zinc/air fuel cell after the discharge; One reduction step is arranged at the zinc oxide that reclaims in the one solar energy reaction unit, and is gaseous state zinc as reducing agent with this zinc oxide reduction with carbon monoxide; One cooling step is to form solid zinc with this gaseous state zinc cooling; And an electrode making step, with this solid zinc in order to make the zinc electrode in the zinc/air fuel cell.
Beneficial effect of the present invention is:
The method of reducing of the zinc oxide of a kind of zinc/air fuel cell of the present invention so that zinc oxide reduction is become solid zinc, in order to make zinc electrode, is applied in the zinc/air fuel cell but make the zinc oxide repetitive cycling reclaim.
The method of reducing of the zinc oxide of a kind of zinc/air fuel cell of the present invention reduces this zinc oxide with carbon monoxide, to reduce amount of heat absorption.
The method of reducing of the zinc oxide of a kind of zinc/air fuel cell of the present invention utilizes solar energy to provide reaction required hear rate energy, to reduce the thermal source cost of integrated artistic.
The method of reducing of the zinc oxide of a kind of zinc/air fuel cell of the present invention utilizes zinc oxide is arranged in this solar energy reaction unit in the fluidized bed mode, to promote the diffuser efficiency and the W-response rate of carbon monoxide.
Description of drawings
Fig. 1: the schematic diagram of existing zinc/air fuel cell.
Fig. 2: the flow chart of the method for reducing of the zinc oxide of zinc/air fuel cell of the present invention.
Fig. 3: the process schematic representation of the method for reducing of the zinc oxide of zinc/air fuel cell of the present invention.
Fig. 4: the schematic diagram of solar energy reaction unit of the present invention.
The main element symbol description:
1 solar energy reaction unit, 11 reaction chambers, 12 charging apertures
13 discharging openings, 14 optical inputs, 15 zinc oxide fluidized beds
16 condensers, 2 coolers, 3 Cyclone machines
4 dust arresters, 91 air pole plates, 92 zincode plates
93 electrolyte
Embodiment
For above-mentioned and other purpose of the present invention, feature and advantage can be become apparent, preferred embodiment of the present invention cited below particularly, and conjunction with figs. are described in detail below:
The method of reducing of the zinc oxide of zinc/air fuel cell provided by the present invention, the zinc oxide reduction that reclaims is become solid zinc, again this solid zinc is used to make the zinc electrode of zinc/air fuel cell, but so that the zinc oxide repetitive cycling of zinc/air fuel cell be used in the zinc/air fuel cell.
Please refer to shown in Figure 2ly, the method for reducing of the zinc oxide of zinc/air fuel cell of the present invention comprises a recycling step S1, a reduction step S2, a cooling step S3 and an electrode making step S4.
Please refer to shown in Figure 2, recycling step S1 of the present invention by the discharge after zinc/air fuel cell in reclaim zinc oxide.More in detail, because zinc/air fuel cell is in discharge process, zinc electrode will be carried out chemical reaction and be formed zinc oxide (ZnO) and be deposited in the electrode, and the chemical equation that it carried out is suc as formula shown in (2) to (4) (the scape technology of passing away part).Therefore, the source of this zinc oxide of present embodiment is preferable after zinc/air fuel cell discharges fully, by reclaiming zinc oxide in this zinc/air fuel cell, to reduce cost of manufacture.
Please refer to shown in Fig. 2 and 3, the zinc oxide that reduction step S2 of the present invention will reclaim is arranged in the solar energy reaction unit 1, and is gaseous state zinc as reducing agent with this zinc oxide reduction with carbon monoxide.More in detail, the zinc oxide that present embodiment reclaims is arranged in this solar energy reaction unit 1, and carbon monoxide fed in this solar energy reaction unit 1, to provide solar energy as reaction energy by this solar energy reaction unit 1, making this carbon monoxide is gaseous state zinc with this zinc oxide reduction.
Wherein, please refer to shown in Figure 4ly, this solar energy reaction unit 1 is provided with a reaction chamber 11, a charging aperture 12, a discharging opening 13, an optical input 14 and a zinc oxide fluidized bed 15.This reaction chamber 11 is arranged in this solar energy reaction unit 1; This charging aperture 12 and discharging opening 13 are communicated with this reaction chamber 11 respectively; This optical input 14 is opened in this solar energy reaction unit 1, imports 1 pair of this reaction cavity 11 of this solar energy reaction unit for solar energy and heats; The zinc oxide of aforementioned this recovery just is set to this zinc oxide fluidized bed 15 with the form of fluidized bed, and this zinc oxide fluidized bed 15 is arranged in this reaction chamber 11.Wherein, preferable the passing through of solar energy imported through this optical input 14 behind a condenser 16 optically focused, and supply reaction institute calorific requirement.
The carbon monoxide of present embodiment preferable under 973～1373K temperature environment the reaction with formula (5) make, also can mix with metal solvent help the reaction carry out:
C
(s)+H
2O
(g)＝CO
(g)+H
2(g) ........(5)
So, the hydrogen that is produced can separate via the applying porous property of catalyst stainless steel film (catalyst-coated porous stainless steel membrane) with carbon monoxide.Hydrogen after the separation can be further used as the fuel of hydrogen fuel cell, perhaps as the required thermal source of follow-up other technologies of gas supply.The carbon monoxide that is obtained then imports in this solar energy reaction unit 1, so that carbon monoxide is oxidized to gaseous state zinc with the zinc oxide that reclaims.
Shown in Fig. 3 and 4, hold above-mentioned, the zinc oxide of this recovery is arranged in this solar energy reaction unit 1 with the form of this zinc oxide fluidized bed 15, this carbon monoxide feeds this reaction chamber 11 by this charging aperture 12, and this zinc oxide fluidized bed 15 of flowing through, evenly mix to contact with zinc oxide, under the temperature environment of 1200～1600K, zinc oxide reduction being become gaseous state zinc, reaction as the formula (6):
ZnO
(s)+CO
(g)＝Zn
(g)+CO
2(g)ΔH
1200K＝185.6kJ/mol.....(6)
Product gaseous state zinc Zn (g) and carbon dioxide CO that reaction is produced
2Just can be by these discharging opening 13 outputs.
So and since the present invention by this solar energy reaction unit 1 supply solar energy as reaction energy, therefore can significantly reduce Yin Gaowen and the thermal source cost that causes; Again and, the zinc oxide of the desire reduction form with this zinc oxide fluidized bed 15 is arranged in this solar energy reaction unit 1, can increase the gas transmission rate of carbon monoxide, therefore in the gas by these discharging opening 13 outputs a small amount of unreacted carbon monoxide is only arranged; Again and, the caloric receptivity Δ H1200K that reacts required with carbon monoxide is lower, also can reduce the hear rate energy that reacts required; Again and, as reducing agent, can increase the mixing efficiency of this carbon monoxide and this zinc oxide with the carbon monoxide of this gaseous state, and then promote reactivity.
Please refer to shown in Fig. 2 and 3, cooling step S3 of the present invention cools off the formation solid zinc with this gaseous state zinc.More in detail, in the present embodiment, just feed in the cooler 2 after the gaseous state zinc that is obtained by formula (6) reaction reduction is discharged by this discharging opening 13,, just can further use to be cooled to granular solid zinc.In addition, the carbon dioxide of being derived by this charging aperture 13 just can be further and calcium oxide (CaO) reaction formation calcium carbonate after cooling, reacts as the formula (7):
CaO
(s)+CO
2(g)→CaCO
3(s) ...............(7)
And the heat that this carbon dioxide and gaseous state zinc are emitted because of cooling just can be used as thermal source other technologies are carried out preheating.
Wherein, because the granular size of this solid zinc is more inhomogeneous, therefore as shown in Figure 3, the preferable screening sequence that carries out again of this solid zinc to obtain the solid zinc that particle is less and be evenly distributed, is fit to be applied to the making of zinc electrode in the zinc/air fuel cell.The screening sequence of present embodiment should cooled solid zinc import in the Cyclone machines 3, and solid zinc particle is bigger by this Cyclone machines 3 is derived by the bottom, and the less solid zinc of particle is derived by the top; The solid zinc that is derived by the top further imports in the dust arrester 4 again, and the subparticle with the solid zinc of the zinc powder that obtains optimum grain-diameter carries out this electrode making step S4 with the solid zinc after this screening as material again.
Please refer to shown in Figure 2, electrode making step S4 of the present invention with this solid zinc in order to make the zinc electrode in the zinc/air fuel cell.More in detail, the solid zinc that present embodiment is obtained this cooling step S3 is made as the zinc electrode of reservation shape by processing modes such as powder metallurgy or castings, for example, if the Powdered mode that then can powder metallurgy of this solid zinc is made as zinc electrode through sintering, further is arranged at zinc/air fuel cell again and uses.So, the present invention just can be by reclaiming zinc oxide in the zinc/air fuel cell, is used in the zinc/air fuel cell again and uses as zinc electrode, with the method for reducing of the zinc oxide of setting up complete zinc/air fuel cell.
The invention provides a kind of method of reducing of zinc oxide of zinc/air fuel cell,,, be applied in the zinc/air fuel cell but make the zinc oxide repetitive cycling reclaim in order to make zinc electrode so that zinc oxide reduction is become solid zinc.
The invention provides a kind of method of reducing of zinc oxide of zinc/air fuel cell, reduce this zinc oxide, to reduce amount of heat absorption with carbon monoxide.
The invention provides a kind of method of reducing of zinc oxide of zinc/air fuel cell, utilize solar energy to provide reaction required hear rate energy, to reduce the thermal source cost of integrated artistic.
The invention provides a kind of method of reducing of zinc oxide of zinc/air fuel cell, utilize zinc oxide is arranged in this solar energy reaction unit in the fluidized bed mode, to promote the diffuser efficiency and the W-response rate of carbon monoxide.
Claims (8)
1. the method for reducing of the zinc oxide of a zinc/air fuel cell is characterized in that comprising:
A recycling step is by reclaiming zinc oxide in the zinc/air fuel cell after the discharge;
A reduction step is arranged at the zinc oxide that reclaims in the solar energy reaction unit, and is gaseous state zinc as reducing agent with this zinc oxide reduction with a carbonoxide;
A cooling step is to form solid zinc with this gaseous state zinc cooling; And
An electrode making step, with this solid zinc in order to make the zinc electrode in the zinc/air fuel cell.
2. according to the method for reducing of the zinc oxide of the described zinc/air fuel cell of claim 1, it is characterized in that, in this reduction step, this zinc oxide is arranged in this solar energy reaction unit with the form of fluidized bed, reduces this zinc oxide for this carbon monoxide this zinc oxide fluidized bed of flowing through.
3. according to the method for reducing of the zinc oxide of the described zinc/air fuel cell of claim 1, it is characterized in that, in this cooling step, further screen this solid zinc with a screening sequence after, carry out this electrode making step again.
4. according to the method for reducing of the zinc oxide of the described zinc/air fuel cell of claim 3, it is characterized in that, this screening sequence feeds a Cyclone machines with this solid zinc, will feed a dust arrester by the solid zinc that this Cyclone machines top obtains again, with the solid zinc after the acquisition screening.
5. according to the method for reducing of the zinc oxide of the described zinc/air fuel cell of claim 1, it is characterized in that in this electrode making step, this solid zinc is made as this zinc electrode in the mode of powder metallurgy or casting.
6. according to the method for reducing of the zinc oxide of the described zinc/air fuel cell of claim 1, it is characterized in that in this reduction step, this carbon monoxide reduces this zinc oxide under the temperature environment of 1200～1600K.
7. according to the method for reducing of the zinc oxide of the described zinc/air fuel cell of claim 1, it is characterized in that, in this reduction step, form carbon monoxide with reaction equation reaction as follows earlier after, reduce this zinc oxide with this carbon monoxide again:
C
(s)+H
2O
(g)＝CO
(g)+H
2(g)。
8. according to the method for reducing of the zinc oxide of the described zinc/air fuel cell of claim 1, it is characterized in that the solar energy that this solar energy reaction unit is provided is imported in this solar energy reaction unit earlier again behind a condenser optically focused.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010190880 CN102270777B (en) | 2010-06-03 | 2010-06-03 | Reduction method for zinc oxide of zinc-air fuel cell |
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|---|---|---|---|
| CN 201010190880 CN102270777B (en) | 2010-06-03 | 2010-06-03 | Reduction method for zinc oxide of zinc-air fuel cell |
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| Publication Number | Publication Date |
|---|---|
| CN102270777A true CN102270777A (en) | 2011-12-07 |
| CN102270777B CN102270777B (en) | 2013-06-05 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103378385A (en) * | 2012-04-23 | 2013-10-30 | 夏普株式会社 | Metal-air battery and energy system |
| CN110446800A (en) * | 2016-06-06 | 2019-11-12 | 兰州金福乐生物工程有限公司 | A kind of aluminium air fuel cell aluminium hydroxide solar heat reduction apparatus |
| CN112751015A (en) * | 2019-10-31 | 2021-05-04 | 青岛海尔智能技术研发有限公司 | Zinc cathode and preparation method thereof, zinc-air battery and direct current water heater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470657A (en) * | 2002-07-25 | 2004-01-28 | 宝钢集团上海梅山有限公司 | Steel making and iron making superlow zine dust recovery and treatment process |
| CN101017031A (en) * | 2007-02-27 | 2007-08-15 | 易继先 | Solar energy heat collection box |
-
2010
- 2010-06-03 CN CN 201010190880 patent/CN102270777B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470657A (en) * | 2002-07-25 | 2004-01-28 | 宝钢集团上海梅山有限公司 | Steel making and iron making superlow zine dust recovery and treatment process |
| CN101017031A (en) * | 2007-02-27 | 2007-08-15 | 易继先 | Solar energy heat collection box |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103378385A (en) * | 2012-04-23 | 2013-10-30 | 夏普株式会社 | Metal-air battery and energy system |
| CN103378385B (en) * | 2012-04-23 | 2016-04-27 | 夏普株式会社 | Metal-air battery and energy resource system |
| US9705164B2 (en) | 2012-04-23 | 2017-07-11 | Sharp Kabushiki Kaisha | Metal-air battery and energy system |
| CN110446800A (en) * | 2016-06-06 | 2019-11-12 | 兰州金福乐生物工程有限公司 | A kind of aluminium air fuel cell aluminium hydroxide solar heat reduction apparatus |
| CN110446800B (en) * | 2016-06-06 | 2021-12-17 | 兰州金福乐生物工程有限公司 | Aluminum hydroxide solar thermal reduction device of aluminum air fuel cell |
| CN112751015A (en) * | 2019-10-31 | 2021-05-04 | 青岛海尔智能技术研发有限公司 | Zinc cathode and preparation method thereof, zinc-air battery and direct current water heater |
| CN112751015B (en) * | 2019-10-31 | 2022-07-26 | 青岛海尔智能技术研发有限公司 | Zinc cathode and preparation method thereof, zinc-air battery and direct current water heater |
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|---|---|
| CN102270777B (en) | 2013-06-05 |
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Granted publication date: 20130605 Termination date: 20140603 |