CN102270777B - 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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- CN102270777B CN102270777B CN 201010190880 CN201010190880A CN102270777B CN 102270777 B CN102270777 B CN 102270777B CN 201010190880 CN201010190880 CN 201010190880 CN 201010190880 A CN201010190880 A CN 201010190880A CN 102270777 B CN102270777 B CN 102270777B
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- zinc
- fuel cell
- zinc oxide
- air fuel
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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 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 subject 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 carries out is suc as formula shown in (1):
The anode reaction that this zincode plate 92 carries out is suc as formula shown in (2):
Zn(s)+2OH
-→ZnO+H
2O+2e
-E
0＝1.25V……..(2)
It reacts only suc as formula shown in (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 aforementioned, 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 zinc/air fuel cell, and take solid carbon (C) with zinc oxide reduction as zinc, the zinc that reduction obtains just can be done further application.At the temperature of 1200K, with the reduction reaction of solid carbon reduction-oxidation zinc suc as formula shown in (4):
ZnO
(s)+C
(s)→Zn
(g)+CO
(g)，ΔH
1200K＝367.4kJ/mol........(4)
Yet, higher as the caloric receptivity Δ H1200K of reducing agent reduction-oxidation zinc with solid carbon, therefore need to 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 easily has the not shortcoming of complete reaction of solid carbon; Again and, due to more than the temperature of carrying out above-mentioned reduction reaction need reach 1200K, at present with various fuel or gas heating to the high temperature of this 1200K, cause the thermal source cost relatively to improve many; Again and, do not set up at present the zinc oxide circulation recycling in zinc/air fuel cell in the method for 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, with the method for reducing of zinc oxide that a kind of zinc/air fuel cell is provided, be applied to the purpose that is fabricated to of zinc/air fuel cell with the zinc that zinc oxide reduction is obtained.
The present invention's time purpose is to provide 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 is to provide 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 discharge; One reduction step is arranged at the zinc oxide that reclaims in one solar energy reaction unit, and take carbon monoxide as reducing agent with this zinc oxide reduction as gaseous state zinc; One cooling step is with the cooling formation solid zinc of this gaseous state zinc; And an electrode fabrication step, with this solid zinc in order to make the zinc electrode in 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 making zinc electrode, but makes zinc oxide repetitive cycling recycle in zinc/air fuel cell.
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 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 chamber 12 charging apertures
13 discharging opening 14 optical input 15 zinc oxide fluidized beds
16 condenser 2 cooler 3 Cyclone machines
4 dust arrester 91 air pole plate 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 cooperation accompanying drawing 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 be used for is made the zinc electrode of zinc/air fuel cell, but so that the zinc oxide repetitive cycling of zinc/air fuel cell be used in 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 fabrication 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.In more detail, due to zinc/air fuel cell in discharge process, zinc electrode will be carried out chemical reaction and formed zinc oxide (ZnO) and be deposited in electrode, and its chemical equation that carries 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 the present embodiment is better 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 a solar energy reaction unit 1, and take carbon monoxide as reducing agent with this zinc oxide reduction as gaseous state zinc.In more detail, the zinc oxide that the present embodiment reclaims is arranged in this solar energy reaction unit 1, and carbon monoxide is passed 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 respectively this reaction chamber 11; This optical input 14 is opened in this solar energy reaction unit 1, inputs 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, better the passing through of solar energy inputted through this optical input 14 after condenser 16 optically focused, and institute's calorific requirement is reacted in supply.
The carbon monoxide of the present embodiment better 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 produces can separate via the applying porous property of catalyst stainless steel film (catalyst-coated porous stainless steel membrane) with carbon monoxide.Hydrogen after separation can be further used as the fuel of hydrogen fuel cell, perhaps as the required thermal source of follow-up other techniques of gas supply.The carbon monoxide that obtains 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 passes into this reaction chamber 11 by this charging aperture 12, and this zinc oxide fluidized bed 15 of flowing through, evenly mix contacting with zinc oxide, zinc oxide reduction is become gaseous state zinc under the temperature environment of 1200～1600K, reaction is suc as formula shown in (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 produces
2Just can be by these discharging opening 13 outputs.
So, due to 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 wish 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 carries out cooling formation solid zinc with this gaseous state zinc.In more detail, in the present embodiment, just pass in a cooler 2 after being discharged by this discharging opening 13 by the gaseous state zinc of formula (6) reaction reduction acquisition, to be cooled to granular solid zinc, just can further use.In addition, the carbon dioxide of being derived by this charging aperture 13 just can further form calcium carbonate with calcium oxide (CaO) reaction after cooling, and reaction is suc as formula shown in (7):
CaO
(s)+CO
2(g)→CaCO
3(s) ...............(7)
And this carbon dioxide and gaseous state zinc carry out preheating because cooling heat of emitting just can be used as thermal source to other techniques.
Wherein, because the granular size of this solid zinc is more inhomogeneous, therefore as shown in Figure 3, the better 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 zinc/air fuel cell.The screening sequence of the present embodiment should cooled solid zinc import in a Cyclone machines 3, and solid zinc particle is larger 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 a dust arrester 4 again, with the subparticle of the solid zinc of the zinc powder that obtains optimum grain-diameter, then carries out this electrode fabrication step S4 with the solid zinc after this screening as material.
Please refer to shown in Figure 2, electrode fabrication step S4 of the present invention with this solid zinc in order to make the zinc electrode in zinc/air fuel cell.In more detail, the present embodiment is made as the zinc electrode of reservation shape with the solid zinc that this cooling step S3 obtains by processing modes such as powder metallurgy or castings, for example, if the Powdered mode that can powder metallurgy of this solid zinc is made as zinc electrode through sintering, more further is arranged at zinc/air fuel cell and uses.So, the present invention just can be by reclaiming zinc oxide in zinc/air fuel cell, recycles in zinc/air fuel cell and use 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, so that zinc oxide reduction is become solid zinc, in order to making zinc electrode, but make zinc oxide repetitive cycling recycle in zinc/air fuel cell.
The invention provides a kind of method of reducing of zinc oxide of zinc/air fuel cell, reduce this zinc oxide with carbon monoxide, to reduce amount of heat absorption.
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 diffuser efficiency and the W-response rate of carbon monoxide.
Claims (4)
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 discharge;
A reduction step, the zinc oxide that the reclaims form with fluidized bed is arranged in a solar energy reaction unit, and with carbon monoxide as reducing agent, for this carbon monoxide this zinc oxide fluidized bed of flowing through, and be gaseous state zinc with this zinc oxide reduction under the temperature environment of 1200～1600K;
A cooling step, with with the cooling formation solid zinc of this gaseous state zinc, and screen this solid zinc with a screening sequence, this screening sequence passes into a Cyclone machines with this solid zinc, to pass into a dust arrester by the solid zinc of this Cyclone machines top acquisition again, with the solid zinc after the acquisition screening; And
An electrode fabrication step, with the solid zinc after this screening in order to make the zinc electrode in zinc/air fuel cell.
2. comply with the method for reducing of the zinc oxide of zinc/air fuel cell claimed in claim 1, it is characterized in that, in this electrode fabrication step, the solid zinc after this screening is made as this zinc electrode in the mode of powder metallurgy or casting.
3. according to the method for reducing of the zinc oxide of zinc/air fuel cell claimed in claim 1, it is characterized in that, in this reduction step, after first forming carbon monoxide with reaction equation reaction as follows, then reduce this zinc oxide with this carbon monoxide:
C
(s)+H
2O
(g)=CO
(g)+H
2(g)。
4. comply with the method for reducing of the zinc oxide of zinc/air fuel cell claimed in claim 1, it is characterized in that, the solar energy that this solar energy reaction unit provides is first inputted after a condenser optically focused in this solar energy reaction unit again.
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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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|---|---|
| CN102270777A CN102270777A (en) | 2011-12-07 |
| CN102270777B true CN102270777B (en) | 2013-06-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5396506B2 (en) * | 2012-04-23 | 2014-01-22 | シャープ株式会社 | Metal-air battery and energy system |
| WO2017211156A1 (en) * | 2016-06-06 | 2017-12-14 | 兰州金福乐生物工程有限公司 | Aluminum hydroxide solar powered thermal reduction device for aluminum-air fuel cell |
| 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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| 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 |
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Granted publication date: 20130605 Termination date: 20140603 |