CA2120775C - Hydrogen removal system for metal/air fuel cell - Google Patents
Hydrogen removal system for metal/air fuel cell Download PDFInfo
- Publication number
- CA2120775C CA2120775C CA002120775A CA2120775A CA2120775C CA 2120775 C CA2120775 C CA 2120775C CA 002120775 A CA002120775 A CA 002120775A CA 2120775 A CA2120775 A CA 2120775A CA 2120775 C CA2120775 C CA 2120775C
- Authority
- CA
- Canada
- Prior art keywords
- air
- electrolyte
- hydrogen
- metal
- storage tank
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000446 fuel Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 66
- 238000007872 degassing Methods 0.000 claims abstract description 27
- 238000003860 storage Methods 0.000 claims abstract description 23
- 238000010926 purge Methods 0.000 claims abstract description 18
- 239000003518 caustics Substances 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000003595 mist Substances 0.000 claims abstract description 13
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 230000003134 recirculating effect Effects 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000003570 air Substances 0.000 description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 halide salts Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
- H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/70—Arrangements for stirring or circulating the electrolyte
- H01M50/77—Arrangements for stirring or circulating the electrolyte with external circulating path
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Fuel Cell (AREA)
Abstract
A metal/air fuel cell is described in which hydrogen is effectively removed from a cell stack and electrolyte storage tank without emitting caustic vapour or mist. The fuel cell comprises: (a) a fuel cell assembly housing, (b) a plurality of metal/air cells disposed in the housing, (c) an electrolyte storage tank, (d) a recirculation loop for continuously recirculating electrolyte from the storage tank through the metal/air cells, (e) air injection means for flowing air between the metal/air cells, (f) a degassing vessel connected to the recirculating loop to receive electrolyte containing hydrogen gas from the metal/air cells, the vessel being ar-ranged to discharge hydrogen gas through a top opening and discharge electrolyte through a bottom outlet for return to the sto-rage tank and this vessel being further arranged to have at least the top portion thereof bathed in air which has passed between the metal/air cells, (g) purging air means adapted to pass air through the electrolyte storage tank and then through the degassing vessel, said purging air serving to dilute the hydrogen and to remove hydrogen from the storage tank, (h) a gas discharge conduit for drawing off purge air and hydrogen discharging from the degassing vessel and (i) filter means connected to said discharge conduit for removing caustic vapour or mist from the discharging purge air and hydrogen.
Description
2 ~ ~ ~ ~ ~ ;~ ~ PGT/CA92/00429 roc~en Removal System for Meta1/Air Fuel Cell Technical Field The invention relates to metal/air fuel cells, and particularly to a hydrogen removal system for such fuel cells having recirculating electrolyte.
Background Art Metal/air fuel cells or batteries produce electricity by the electro-chemical coupling of a reactive metallic anode to an air cathode through a suitable electrolyte in a cell. The air cathode is typically a sheet-like member, having opposite surfaces respectively exposed to air and w -to the aqueous electrolyte of the cell. During cell operation, oxygen is reduced within the cathode while metal of the anode is oxidized, providing a usable electric current flow through external circuitry connected between the anode and cathode. The air cathode must be permeable to air but substantially impermeable to aqueous electrolyte, and must incorporate an electrically conductive element to which the external circuitry can be connected. Present-day commercial air cathodes are commonly constituted of active carbon (with or without an added dissociation-promoting catalyst) in association with a finely divided hydrophobic polymeric material and incorporating a metal screen as the conductive element. A
variety of anode metals have been used or proposed; among them, zinc, alloys of aluminum and alloys of magnesium are considered especially advantageous for particular applications, owing to their low cost, light weight and ability to function as anodes in metal/air fuel cells using a variety of electrolytes.
A typical aluminum/air cell comprises a body of . aqueous electrolyte, a sheet-like air cathode having one surface exposed to the electrolyte and the other surface exposed to air, and an aluminum alloy anode member (e.g. a flat plate) immersed in the electrolyte in facing spaced relation to the first-mentioned cathode surface. A
_.....-~~"..,..._......~..w....~e..,~r......e.<,r...< ru.......rr i;m.~ra-...r.atr..au.ra~c...v. r!~:.'.~..~_":fCfwSR':,:6,ur~n.. v,'~, i25 fp:: ;a'f>
rf."~~. . . , a.... . ..
typical fuel cell unit or battery comprises a plurality of such cells.
Aqueous electrolytes for metal-air fuel cells consist of two basic types, namely a neutral-pH electrolyte and a highly alkaline electrolyte. The neutral-pH electrolyte usually contains halide salts and, because of its relatively low electrical conductivity and the virtual insolubility of aluminum therein, is used for relatively low power applications. The highly alkaline electrolyte usually consists of NaOH or KOH solution, and yields a higher cell voltage than the neutral electrolyte.
In alkaline electrolytes, the cell discharge reaction may be written:
4A1 + 303 + 6H20 + 4 KOH ~ 4A1 (OH) ~ + K' . (liquid solution), followed,~after the dissolved potassium (or sodium) aluminate exceeds saturation level, by:
4Al(OIi)~ + 4K' -~ 4A1(OH)3 (solid) + 4KOH
In addition to the above oxygen-reducing reactions, there is also an undesirable, non-beneficial reaction of aluminum in both types of electrolyte to form hydrogen, as follows:
2A1 + 6H20 -~ 2A1(OH)3 + 3H2 (gas) When a metal/air fuel cell is operated, quantities of hydrogen form from the surface of the anode. As with other fuel cells or batteries this hydrogen can reach explosive concentrations.
Metal/air fuel cells are of particular interest as a fuel source for motorized vehicles and when they are used for this purpose it is important to keep the hydrogen level in the fuel'cell, vehicle and vehicle surroundings below the flammable limit of about 4% by volume. Also when the cells are used in vehicles, the low hydrogen level must be achieved without emitting caustic vapour or mist from the system.
A battery intended as an emergency power supply is described in U.S. Patent No. 4,490,443, issued December WO 93/07652 ~, ~, ,~, ~ r~ ~ PCT/CA92/00429 25, 1984. That battery uses a plurality of individual metal air cells with an electrolyte --recirculated through the cells by means of'a centrifugal or impeller Bump. It is capable of operating under high load, but it has a major disadvantage in that it does not provide a ~ satisfactory means for avoiding hydrogen build-up in the electrolyte reservoir.
U.S. Patent 4,994,332 describes another form of metal/air battery with an alkali metal hydroxide electrolyte circulating through battery cells by means of a pump. The electrolyte exiting from the cells is fed to a knock-out vessel for hydrogen removal from the system.
The hydrogen is discharged through an, exhaust line.
U.S. Patent 4,950,561 describes a metal/air battery with multiple cells which again recognizes the problem of hydrogen generation in the cells. In that design, the hydrogen gas which is generated either flows with the electrolyte or is exhausted through the electrolyte outlet line into an electrolyte reservoit.
. It is the object of the present invention to develop a battery system capable of effectively removing hydrogen from a fuel cell and its electrolyte storage tank without emitting caustic vapour or mist~'-from the system.
Disclosure of the Invention . 25 The present invention in its broadest aspect relates to a metal/air fuel cell assembly comprising:
(a) a fuel cell assembly housing, (b) a plurality of metal/air cells disposed in the housing, (c) an electrolyte storage tank, , (d) a recirculation loop for continuously recirculating electrolyte from the storage tank through the metal/air cells, ~e~ air injection means for flowing air between the metal/air cells, (f) a degassing vessel connected to the recirculating loop to receive electrolyte containing hydrogen gas from the metal/air cells, the vessel being arranged to N d ~.,~.
:-P w.
v' 'ii. .~:'f.
;, !!«. ~ -..Ll....... ,:S ..' .:. f . _,a.:i'.. ~:a r... 7 ~ ,r~ ..
n .< .
Y
vr: Cs. ..~~r, .>. ...r~ , ...c,-. ,r.:,~
,: et - o;,.: t°:~
-:.~., .: .'..r:. ,.. . . r~ ~ ,., .,T. w. d'4s... r1... .~C..~~, n :f. .sFr .
..-0' . a "~"n , v -0 .d ..
."t ... ~sla.. .
s .:. o..I.' !.:~.r r!..
i... --f ~ ~.'.i ., a r~' . J' r:. ~
. ,r r .
,.."_.. .:F. '~ ,: -~s'.,_ r.~:',-.
r, , ..r..., .r , r~
re~ .~. ,. .1.., . . . 'c..: . . ..
.f:..,r . ... , ..f. ':_;; ,.,.. _ ... ~. , '-.-'E:.
...........?.........~'s._.....,r <a~~.... ...., ,.. a. ,.... ,....._.r::~h ...>x:..;...1...._.........:.~X~z...::::..,..G~.:...'-,..~~.s~...... ..., ...
Background Art Metal/air fuel cells or batteries produce electricity by the electro-chemical coupling of a reactive metallic anode to an air cathode through a suitable electrolyte in a cell. The air cathode is typically a sheet-like member, having opposite surfaces respectively exposed to air and w -to the aqueous electrolyte of the cell. During cell operation, oxygen is reduced within the cathode while metal of the anode is oxidized, providing a usable electric current flow through external circuitry connected between the anode and cathode. The air cathode must be permeable to air but substantially impermeable to aqueous electrolyte, and must incorporate an electrically conductive element to which the external circuitry can be connected. Present-day commercial air cathodes are commonly constituted of active carbon (with or without an added dissociation-promoting catalyst) in association with a finely divided hydrophobic polymeric material and incorporating a metal screen as the conductive element. A
variety of anode metals have been used or proposed; among them, zinc, alloys of aluminum and alloys of magnesium are considered especially advantageous for particular applications, owing to their low cost, light weight and ability to function as anodes in metal/air fuel cells using a variety of electrolytes.
A typical aluminum/air cell comprises a body of . aqueous electrolyte, a sheet-like air cathode having one surface exposed to the electrolyte and the other surface exposed to air, and an aluminum alloy anode member (e.g. a flat plate) immersed in the electrolyte in facing spaced relation to the first-mentioned cathode surface. A
_.....-~~"..,..._......~..w....~e..,~r......e.<,r...< ru.......rr i;m.~ra-...r.atr..au.ra~c...v. r!~:.'.~..~_":fCfwSR':,:6,ur~n.. v,'~, i25 fp:: ;a'f>
rf."~~. . . , a.... . ..
typical fuel cell unit or battery comprises a plurality of such cells.
Aqueous electrolytes for metal-air fuel cells consist of two basic types, namely a neutral-pH electrolyte and a highly alkaline electrolyte. The neutral-pH electrolyte usually contains halide salts and, because of its relatively low electrical conductivity and the virtual insolubility of aluminum therein, is used for relatively low power applications. The highly alkaline electrolyte usually consists of NaOH or KOH solution, and yields a higher cell voltage than the neutral electrolyte.
In alkaline electrolytes, the cell discharge reaction may be written:
4A1 + 303 + 6H20 + 4 KOH ~ 4A1 (OH) ~ + K' . (liquid solution), followed,~after the dissolved potassium (or sodium) aluminate exceeds saturation level, by:
4Al(OIi)~ + 4K' -~ 4A1(OH)3 (solid) + 4KOH
In addition to the above oxygen-reducing reactions, there is also an undesirable, non-beneficial reaction of aluminum in both types of electrolyte to form hydrogen, as follows:
2A1 + 6H20 -~ 2A1(OH)3 + 3H2 (gas) When a metal/air fuel cell is operated, quantities of hydrogen form from the surface of the anode. As with other fuel cells or batteries this hydrogen can reach explosive concentrations.
Metal/air fuel cells are of particular interest as a fuel source for motorized vehicles and when they are used for this purpose it is important to keep the hydrogen level in the fuel'cell, vehicle and vehicle surroundings below the flammable limit of about 4% by volume. Also when the cells are used in vehicles, the low hydrogen level must be achieved without emitting caustic vapour or mist from the system.
A battery intended as an emergency power supply is described in U.S. Patent No. 4,490,443, issued December WO 93/07652 ~, ~, ,~, ~ r~ ~ PCT/CA92/00429 25, 1984. That battery uses a plurality of individual metal air cells with an electrolyte --recirculated through the cells by means of'a centrifugal or impeller Bump. It is capable of operating under high load, but it has a major disadvantage in that it does not provide a ~ satisfactory means for avoiding hydrogen build-up in the electrolyte reservoir.
U.S. Patent 4,994,332 describes another form of metal/air battery with an alkali metal hydroxide electrolyte circulating through battery cells by means of a pump. The electrolyte exiting from the cells is fed to a knock-out vessel for hydrogen removal from the system.
The hydrogen is discharged through an, exhaust line.
U.S. Patent 4,950,561 describes a metal/air battery with multiple cells which again recognizes the problem of hydrogen generation in the cells. In that design, the hydrogen gas which is generated either flows with the electrolyte or is exhausted through the electrolyte outlet line into an electrolyte reservoit.
. It is the object of the present invention to develop a battery system capable of effectively removing hydrogen from a fuel cell and its electrolyte storage tank without emitting caustic vapour or mist~'-from the system.
Disclosure of the Invention . 25 The present invention in its broadest aspect relates to a metal/air fuel cell assembly comprising:
(a) a fuel cell assembly housing, (b) a plurality of metal/air cells disposed in the housing, (c) an electrolyte storage tank, , (d) a recirculation loop for continuously recirculating electrolyte from the storage tank through the metal/air cells, ~e~ air injection means for flowing air between the metal/air cells, (f) a degassing vessel connected to the recirculating loop to receive electrolyte containing hydrogen gas from the metal/air cells, the vessel being arranged to N d ~.,~.
:-P w.
v' 'ii. .~:'f.
;, !!«. ~ -..Ll....... ,:S ..' .:. f . _,a.:i'.. ~:a r... 7 ~ ,r~ ..
n .< .
Y
vr: Cs. ..~~r, .>. ...r~ , ...c,-. ,r.:,~
,: et - o;,.: t°:~
-:.~., .: .'..r:. ,.. . . r~ ~ ,., .,T. w. d'4s... r1... .~C..~~, n :f. .sFr .
..-0' . a "~"n , v -0 .d ..
."t ... ~sla.. .
s .:. o..I.' !.:~.r r!..
i... --f ~ ~.'.i ., a r~' . J' r:. ~
. ,r r .
,.."_.. .:F. '~ ,: -~s'.,_ r.~:',-.
r, , ..r..., .r , r~
re~ .~. ,. .1.., . . . 'c..: . . ..
.f:..,r . ... , ..f. ':_;; ,.,.. _ ... ~. , '-.-'E:.
...........?.........~'s._.....,r <a~~.... ...., ,.. a. ,.... ,....._.r::~h ...>x:..;...1...._.........:.~X~z...::::..,..G~.:...'-,..~~.s~...... ..., ...
discharge hydrogen gas through a top opening and discharge electrolyte through a bottom outlet for return to the storage tank and this vessel being further arranged to have at least the top portion thereof bathed in air which has passed between the metal/air cells, (g) purging air means adapted to pass air through the electrolyte storage tank and then through the degassing vessel, said purging air serving to dilute the hydrogen and to remove hydrogen from the storage tank, (h) a gas discharge conduit for drawing off purge air and hydrogen discharging from the degassing vessel and (i) filter means connected to said discharge conduit for removing caustic vapour or mist from the discharging purge air and hydrogen.
With the system of this invention, the hydrogen which is generated at the anode surfaces is carried out of the metal/air cells by the recirculating electrolyte and most of the hydroge» in the electrolyte is removed in the degassing vessel. Most of the hydrogen is removed by a series of preferably angled baffles covered with a porous non-woven material offering high surface area, e.g. 3M
Scotchbritee. Residual hydrogen in the form of very small bubbles, typically about 4% by volume, is carried back to the electrolyte storage tank with the recycled electrolyte from the degassing vessel. This hydrogen gradually evolves from the liquid in the storage tank arid the purging air system is used to purge the top of the storage tank with air to keep the hydrogen level below about 2%.
When the fuel cell is used in a vehicle, some liquid is inevitably entrained in the purge air stream because of vehicla motion and this is carried with the air back to the degassing vessel.
The degassing vessel is preferably positioned within the battery housing together with the metal/air cells such that the degassing vessel may be bathed in a stream of the air exhausting from between the metal/air cells. This air picks up and dilutes the hydrogen evolving from the WO 93/07652 ~ 212 0 '~ ~ J PCT/CA92/00429 S
degassing vessel and this mixture of air and hydrogen, also containing caustic vapour or mist, is discharged through a discharge conduit. To avoid contaminating the atmosphere, the discharging air and hydrogen is filtered first by a coarse non-woven filter, e.g. Scotchbrite~
material available from 3M Co. and then by a fine automotive-type air intake paper filter before being exhausted into the atmosphere. The coarse non-woven filter removes droplets of caustic, while the filter paper removes any very fine mist particles. This system provides excellent odour control with no noticeable caustic mist.
Brief Descr~~tion of the Drawi;dos Further features of the present invention will become apparent to those skilled in the art to which the present invention relates from reading the following specification with reference to the accompanying drawings, in which:
Fig. 1 is a schematic flow diagram illustrating a preferred embodiment of the present invention;
Fig. 2 is an end elevation in partial section showing a fuel cell according t~ this invention:
Fig. 3 is a side elevation in partial section showing ' the fuel cell of Fig. 2:
Fig. 4 is a sectional elevation of an electrolyte/gas ~5 separator vessel;
Fig. 5 is a sectional view along line V-V of Fig. 4:
Fig. 6 is a top plan view of a refuelling rack; and Fig. 7 is a partial sectional view showing an electrolyte feed arrangement.
Best Mode for Carrvina Out the Invention The present invention is particularly useful in an electrolyte circulation system for an aluminum/air fuel cell.
The general concept of this invention is illustrated by the schematic flow sheet of Figure 1 which shows a main fuel cell. case or housing 10 containing aluminum-air fuel cell stacks 11. Alkaline electrolyte, e.g. a solution of NaOH or KOH, is stored in storage tank 12 and is pumped via inlet line 13 and pump 14 into the bottom of the aluminum-air cells. The used electrolyte is returned via electrolyte return line 15 and recycle pump 16. Air is fed to the fuel cell stacks 11 by an air feed pump 19.
The fuel cell generates hydrogen and some of this is trapped in the electrolyte in the form of very small bubbles. A mixture of electrolyte and hydrogen discharges through top outlet 17 into an electrolyte/gas separator or degassing vessel 18. The electrolyte is largely degassed in this vessel with the separating hydrogen passing upwardly through air open top. It proceeds through outlet and into a filter assembly 21 for removing caustic mist and caustic droplets with hydrogen and air substantially 15 free of caustic being discharged to the atmosphere through discharge outlet 22.
The electrolyte in the degassing vessel 18 continues to contain some residual hydrogen in the form of very small bubbles, typically in the amount of about 4% by 20 volume, and this is carried back to reservoir 12 through return line 15. In the reservoir, the hydrogen gradually separates from the liquid. In order to keep the concentration of hydrogen in the space above the electrolyte in storage tank 12 below about 2% by volume, purge air is pumped into the top of tank 12 by way of air pump 23 and air line 24. This purge air dilutes and collects hydrogen from tank 1.2 and this mixture then passes via purge line 25 back to the degassing vessel 18.
This degassing vessel 18 is also bathed in a stream of air originating from air feed 19 and exhausting from the aluminum-air cells 11 and the air which is discharged through outlet 20 is a mixture of the air exhausting from the aluminum-air cells 11 and the purge air from line 25.
The various components of the flow sheet of Figure 1 will now be described in greater detail with reference to Figure 2 to 7. As can be seen from Figures 2 and 3, the fuel cell housing 10 contains 4 stacks of aluminum-air WO 93/07652 ~ ~ ~ ~ ~ ~ '~ PCT/CA92/00429 cells 35 with each stack containing 14 such aluminum-air cells thereby providing a total of 56 cells in the complete fuel cell assembly. In this particular unit, each anode has an area of approximately 950 cm2 and the electrolyte circulates at a rate of about 25 1/min, giving a total power output of about 8 Kw.
The fuel cell housing 10 includes a bottom wall 30, side wall 31, a top wall 32 and end wall 33. These are made from a chemical resistant plastic material, such as polyvinylchloride or polyphenylene oxide. The aluminum-air cells 35 are each made up of cathode walls 36 with air gaps 37 therebetween for the passage of oxidizing air.
Tlie cathode walls 36 also form therebetween electrolyte passages 38 through which electrolyte moves from bottom to top. Each of these electrolyte passages 38 contains an aluminum anode 39 which is mounted at the top end thereof to top wall 32 with an electrical connector 65 passing from each anode 39 up through the top wall 32 and connecting to an anode busbar 40.- The electrical connection to the cathodes is made by way of cathode connector tabs 41.
The electrolyte being pumped from the reservoir 12 enters the fuel cell via inlet 42 and it travels along manifold 43 in the bottom region of the housing.
extending from this manifold 43 are a series of flow tubes 44 with one of these flow tubes being used for each aluminum-air cell as can be seen fry:: Fig. 7. The electrolyte enters each aluminum-air cell by way of individual flow passages 45.
As shown in Figure 2, the used electrolyte and hydrogen gas discharge through top outlet 17 and into an electrolyte/gas separator or degassing vessel 18.
The degassing vessel 18 can be seen in Figure 2 between the two'~longitudinal stacks of aluminum-air cells as a long narrow reservoir. It is described in greater detail in Figures 4 and 5 where it is seen to include a bottom wall 48, end walls 49, side walls 50 and divider WO 93/07652 PC'T/CA92/00429 walls 51 extending downwardly from the top of the separator vessel while being spaced from the bottom 48 thereof. The separator vessel contains downwardly sloped baffles 52 covered with a porous non-woven material offering high surface area, e.g. 3M Scotchbrite~. The mixture of electrolyte and gas entering the degassing vessel 18 from the aluminum-air cells flows over the baffles and drains into the degassing vessel. The purge air stream 25 enters the degassing vessel via inlet 53 positioned below the baffles 52. The electrolyte 54 being recycled to the storage tank is discharged from the gas separator through outlet 55.
The mixture of air, hydrogen, caustic mist and caustic particles rising from the degassing vessel 18 traveled through discharge outlet 47 and then passes through the exhaust filter 21 mounted on top of the fuel cell housing 10. This filter includes side walls 57 and 59, an intermediate wall 58, a bottom wall 60 between walls 58 and 59 and an inclined top wall 61. The exhaust gases enter between walls 57 and 58 and the clean air and gas being discharged exits through outlets 22. The inlet portion includes a filter 63 made of pads of Scotchbrite~
material for filtering out caustic droplets and an automotive air-intake paper filter 64 for removing any fine mist. The gases being discharged through outlet 22 contain little or no caustic mist or droplets.
From the above description of a preferred embodiment of the invention, those skilled in the art will perceive improvements, changes and modifications. Such improvements, changes and modifications within the skill of the art are intended to be covered by the appended claims.
With the system of this invention, the hydrogen which is generated at the anode surfaces is carried out of the metal/air cells by the recirculating electrolyte and most of the hydroge» in the electrolyte is removed in the degassing vessel. Most of the hydrogen is removed by a series of preferably angled baffles covered with a porous non-woven material offering high surface area, e.g. 3M
Scotchbritee. Residual hydrogen in the form of very small bubbles, typically about 4% by volume, is carried back to the electrolyte storage tank with the recycled electrolyte from the degassing vessel. This hydrogen gradually evolves from the liquid in the storage tank arid the purging air system is used to purge the top of the storage tank with air to keep the hydrogen level below about 2%.
When the fuel cell is used in a vehicle, some liquid is inevitably entrained in the purge air stream because of vehicla motion and this is carried with the air back to the degassing vessel.
The degassing vessel is preferably positioned within the battery housing together with the metal/air cells such that the degassing vessel may be bathed in a stream of the air exhausting from between the metal/air cells. This air picks up and dilutes the hydrogen evolving from the WO 93/07652 ~ 212 0 '~ ~ J PCT/CA92/00429 S
degassing vessel and this mixture of air and hydrogen, also containing caustic vapour or mist, is discharged through a discharge conduit. To avoid contaminating the atmosphere, the discharging air and hydrogen is filtered first by a coarse non-woven filter, e.g. Scotchbrite~
material available from 3M Co. and then by a fine automotive-type air intake paper filter before being exhausted into the atmosphere. The coarse non-woven filter removes droplets of caustic, while the filter paper removes any very fine mist particles. This system provides excellent odour control with no noticeable caustic mist.
Brief Descr~~tion of the Drawi;dos Further features of the present invention will become apparent to those skilled in the art to which the present invention relates from reading the following specification with reference to the accompanying drawings, in which:
Fig. 1 is a schematic flow diagram illustrating a preferred embodiment of the present invention;
Fig. 2 is an end elevation in partial section showing a fuel cell according t~ this invention:
Fig. 3 is a side elevation in partial section showing ' the fuel cell of Fig. 2:
Fig. 4 is a sectional elevation of an electrolyte/gas ~5 separator vessel;
Fig. 5 is a sectional view along line V-V of Fig. 4:
Fig. 6 is a top plan view of a refuelling rack; and Fig. 7 is a partial sectional view showing an electrolyte feed arrangement.
Best Mode for Carrvina Out the Invention The present invention is particularly useful in an electrolyte circulation system for an aluminum/air fuel cell.
The general concept of this invention is illustrated by the schematic flow sheet of Figure 1 which shows a main fuel cell. case or housing 10 containing aluminum-air fuel cell stacks 11. Alkaline electrolyte, e.g. a solution of NaOH or KOH, is stored in storage tank 12 and is pumped via inlet line 13 and pump 14 into the bottom of the aluminum-air cells. The used electrolyte is returned via electrolyte return line 15 and recycle pump 16. Air is fed to the fuel cell stacks 11 by an air feed pump 19.
The fuel cell generates hydrogen and some of this is trapped in the electrolyte in the form of very small bubbles. A mixture of electrolyte and hydrogen discharges through top outlet 17 into an electrolyte/gas separator or degassing vessel 18. The electrolyte is largely degassed in this vessel with the separating hydrogen passing upwardly through air open top. It proceeds through outlet and into a filter assembly 21 for removing caustic mist and caustic droplets with hydrogen and air substantially 15 free of caustic being discharged to the atmosphere through discharge outlet 22.
The electrolyte in the degassing vessel 18 continues to contain some residual hydrogen in the form of very small bubbles, typically in the amount of about 4% by 20 volume, and this is carried back to reservoir 12 through return line 15. In the reservoir, the hydrogen gradually separates from the liquid. In order to keep the concentration of hydrogen in the space above the electrolyte in storage tank 12 below about 2% by volume, purge air is pumped into the top of tank 12 by way of air pump 23 and air line 24. This purge air dilutes and collects hydrogen from tank 1.2 and this mixture then passes via purge line 25 back to the degassing vessel 18.
This degassing vessel 18 is also bathed in a stream of air originating from air feed 19 and exhausting from the aluminum-air cells 11 and the air which is discharged through outlet 20 is a mixture of the air exhausting from the aluminum-air cells 11 and the purge air from line 25.
The various components of the flow sheet of Figure 1 will now be described in greater detail with reference to Figure 2 to 7. As can be seen from Figures 2 and 3, the fuel cell housing 10 contains 4 stacks of aluminum-air WO 93/07652 ~ ~ ~ ~ ~ ~ '~ PCT/CA92/00429 cells 35 with each stack containing 14 such aluminum-air cells thereby providing a total of 56 cells in the complete fuel cell assembly. In this particular unit, each anode has an area of approximately 950 cm2 and the electrolyte circulates at a rate of about 25 1/min, giving a total power output of about 8 Kw.
The fuel cell housing 10 includes a bottom wall 30, side wall 31, a top wall 32 and end wall 33. These are made from a chemical resistant plastic material, such as polyvinylchloride or polyphenylene oxide. The aluminum-air cells 35 are each made up of cathode walls 36 with air gaps 37 therebetween for the passage of oxidizing air.
Tlie cathode walls 36 also form therebetween electrolyte passages 38 through which electrolyte moves from bottom to top. Each of these electrolyte passages 38 contains an aluminum anode 39 which is mounted at the top end thereof to top wall 32 with an electrical connector 65 passing from each anode 39 up through the top wall 32 and connecting to an anode busbar 40.- The electrical connection to the cathodes is made by way of cathode connector tabs 41.
The electrolyte being pumped from the reservoir 12 enters the fuel cell via inlet 42 and it travels along manifold 43 in the bottom region of the housing.
extending from this manifold 43 are a series of flow tubes 44 with one of these flow tubes being used for each aluminum-air cell as can be seen fry:: Fig. 7. The electrolyte enters each aluminum-air cell by way of individual flow passages 45.
As shown in Figure 2, the used electrolyte and hydrogen gas discharge through top outlet 17 and into an electrolyte/gas separator or degassing vessel 18.
The degassing vessel 18 can be seen in Figure 2 between the two'~longitudinal stacks of aluminum-air cells as a long narrow reservoir. It is described in greater detail in Figures 4 and 5 where it is seen to include a bottom wall 48, end walls 49, side walls 50 and divider WO 93/07652 PC'T/CA92/00429 walls 51 extending downwardly from the top of the separator vessel while being spaced from the bottom 48 thereof. The separator vessel contains downwardly sloped baffles 52 covered with a porous non-woven material offering high surface area, e.g. 3M Scotchbrite~. The mixture of electrolyte and gas entering the degassing vessel 18 from the aluminum-air cells flows over the baffles and drains into the degassing vessel. The purge air stream 25 enters the degassing vessel via inlet 53 positioned below the baffles 52. The electrolyte 54 being recycled to the storage tank is discharged from the gas separator through outlet 55.
The mixture of air, hydrogen, caustic mist and caustic particles rising from the degassing vessel 18 traveled through discharge outlet 47 and then passes through the exhaust filter 21 mounted on top of the fuel cell housing 10. This filter includes side walls 57 and 59, an intermediate wall 58, a bottom wall 60 between walls 58 and 59 and an inclined top wall 61. The exhaust gases enter between walls 57 and 58 and the clean air and gas being discharged exits through outlets 22. The inlet portion includes a filter 63 made of pads of Scotchbrite~
material for filtering out caustic droplets and an automotive air-intake paper filter 64 for removing any fine mist. The gases being discharged through outlet 22 contain little or no caustic mist or droplets.
From the above description of a preferred embodiment of the invention, those skilled in the art will perceive improvements, changes and modifications. Such improvements, changes and modifications within the skill of the art are intended to be covered by the appended claims.
Claims (4)
1. A fuel cell assembly comprising:
(a) a housing, (b) a plurality of metal/air cells disposed in the housing, (c) an electrolyte storage tank, (d) a recirculation loop for continuously recirculating electrolyte from the storage tank through the metal/air cells, (e) air blower means for flowing air between the metal/air cells, (f) a degassing vessel connected to the recirculating loop to receive electrolyte containing hydrogen gas from the metal/air cells, the vessel being arranged to discharge hydrogen gas through a top opening and discharge electrolyte through a bottom outlet for return to the storage tank and this vessel being further arranged to have at least the top portion thereof bathed in air which has passed between the metal/air cells, (g) purging air means for passing air through the electrolyte storage tank and then through the degassing vessel, said purging air serving to dilute the hydrogen and to remove hydrogen from the storage tank, (h) a gas discharge conduit for drawing off air and hydrogen discharging from the degassing vessel and (i) filter means connected to said discharge conduit for removing caustic vapour or mist from the discharging air and hydrogen.
(a) a housing, (b) a plurality of metal/air cells disposed in the housing, (c) an electrolyte storage tank, (d) a recirculation loop for continuously recirculating electrolyte from the storage tank through the metal/air cells, (e) air blower means for flowing air between the metal/air cells, (f) a degassing vessel connected to the recirculating loop to receive electrolyte containing hydrogen gas from the metal/air cells, the vessel being arranged to discharge hydrogen gas through a top opening and discharge electrolyte through a bottom outlet for return to the storage tank and this vessel being further arranged to have at least the top portion thereof bathed in air which has passed between the metal/air cells, (g) purging air means for passing air through the electrolyte storage tank and then through the degassing vessel, said purging air serving to dilute the hydrogen and to remove hydrogen from the storage tank, (h) a gas discharge conduit for drawing off air and hydrogen discharging from the degassing vessel and (i) filter means connected to said discharge conduit for removing caustic vapour or mist from the discharging air and hydrogen.
2. A fuel cell assembly according to claim 1 wherein the degassing vessel is also within said housing.
3. A fuel cell assembly according to claim 2 wherein the degassing vessel contains a plurality of baffles covered with porous, high surface area, non-woven material.
4. A fuel cell assembly according to claim 3 wherein the gas discharge filter means comprises a first stage consisting of a coarse non-woven filter and a second stage consisting of a fine filter paper.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US773,511 | 1991-10-09 | ||
| US07/773,511 US5156925A (en) | 1991-10-09 | 1991-10-09 | Hydrogen removal system for metal/air cell |
| PCT/US1992/000429 WO1992013436A1 (en) | 1991-01-22 | 1992-01-17 | Electronic/electromechanical packaging arrangement for facility management system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2120775A1 CA2120775A1 (en) | 1993-04-15 |
| CA2120775C true CA2120775C (en) | 2003-03-18 |
Family
ID=25098519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002120775A Expired - Fee Related CA2120775C (en) | 1991-10-09 | 1992-09-29 | Hydrogen removal system for metal/air fuel cell |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5156925A (en) |
| CA (1) | CA2120775C (en) |
| WO (1) | WO1993007652A1 (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5356729A (en) * | 1993-06-15 | 1994-10-18 | Aer Energy Resources, Inc. | Diffusion controlled air manager for metal-air battery |
| US5721064A (en) * | 1993-04-30 | 1998-02-24 | Aer Energy Resources Inc. | Air manager system for reducing gas concentrations in a metal-air battery |
| US5429885A (en) * | 1993-11-22 | 1995-07-04 | Yardney Technical Products, Inc. | Hydrogen management system for metal/air fuel cell |
| CA2206952C (en) * | 1994-12-08 | 2002-09-03 | Yardney Technical Products, Inc. | Hydrogen management system for metal/air fuel cell |
| US5563004A (en) * | 1995-03-21 | 1996-10-08 | Aer Energy Resources, Inc. | Rechargeable metal-air electrochemical cell with hydrogen recombination and end-of-charge indicator |
| US5506067A (en) * | 1995-04-04 | 1996-04-09 | Aer Energy Resources, Inc. | Rechargeable electrochemical cell and cell case therefor with vent for use in internal recombination of hydrogen and oxygen |
| US5952117A (en) * | 1996-10-24 | 1999-09-14 | Metallic Power, Inc. | Method and apparatus for refueling an electrochemical power source |
| US6106962A (en) | 1997-09-24 | 2000-08-22 | Aer Energy Resources Inc. | Air manager control using cell voltage as auto-reference |
| FR2770339B1 (en) | 1997-10-27 | 2003-06-13 | Commissariat Energie Atomique | STRUCTURE HAVING FORMED ELECTRIC CONTACTS THROUGH THE SUBSTRATE OF THIS STRUCTURE AND METHOD OF OBTAINING SUCH A STRUCTURE |
| US6653003B1 (en) * | 1999-10-12 | 2003-11-25 | Reveo Inc. | Fuel cell support and electrical interconnector |
| US6406805B1 (en) * | 1999-10-19 | 2002-06-18 | Ford Global Technologies, Inc. | Method for storing purged hydrogen from a vehicle fuel cell system |
| US6329091B1 (en) | 2000-04-14 | 2001-12-11 | Ford Global Technologies, Inc. | Fuel reformer system for a fuel cell |
| US6673136B2 (en) * | 2000-09-05 | 2004-01-06 | Donaldson Company, Inc. | Air filtration arrangements having fluted media constructions and methods |
| US6432177B1 (en) | 2000-09-12 | 2002-08-13 | Donaldson Company, Inc. | Air filter assembly for low temperature catalytic processes |
| US6797027B2 (en) * | 2001-04-11 | 2004-09-28 | Donaldson Company, Inc. | Filter assemblies and systems for intake air for fuel cells |
| US6783881B2 (en) | 2001-04-11 | 2004-08-31 | Donaldson Company, Inc. | Filter assembly for intake air of fuel cell |
| US7416580B2 (en) * | 2001-04-11 | 2008-08-26 | Donaldsom Company, Inc. | Filter assemblies and systems for intake air for fuel cells |
| US6780534B2 (en) | 2001-04-11 | 2004-08-24 | Donaldson Company, Inc. | Filter assembly for intake air of fuel cell |
| DE10139136A1 (en) * | 2001-08-09 | 2003-02-20 | Bayerische Motoren Werke Ag | Method for operating vehicle fuel tank system with liquid hydrogen involves producing pressure drop to ventilate interior space of capsule and further processing leaking gas |
| US20030035984A1 (en) | 2001-08-15 | 2003-02-20 | Colborn Jeffrey A. | Metal fuel cell system for providing backup power to one or more loads |
| US6951697B2 (en) * | 2001-09-11 | 2005-10-04 | Donaldson Company, Inc. | Integrated systems for use with fuel cells, and methods |
| US6689711B2 (en) | 2001-10-09 | 2004-02-10 | Metallic Power, Inc. | Methods of producing oxygen reduction catalyst |
| US6679280B1 (en) | 2001-10-19 | 2004-01-20 | Metallic Power, Inc. | Manifold for fuel cell system |
| US6911274B1 (en) | 2001-10-19 | 2005-06-28 | Metallic Power, Inc. | Fuel cell system |
| US6873157B2 (en) * | 2002-04-04 | 2005-03-29 | Metallic Power, Inc. | Method of and system for determining the remaining energy in a metal fuel cell |
| US6764588B2 (en) * | 2002-05-17 | 2004-07-20 | Metallic Power, Inc. | Method of and system for flushing one or more cells in a particle-based electrochemical power source in standby mode |
| US6942105B2 (en) * | 2002-05-17 | 2005-09-13 | Metallic Power, Inc. | In-line filtration for a particle-based electrochemical power system |
| EP1570537A2 (en) * | 2002-12-02 | 2005-09-07 | Donaldson Company, Inc. | Various filter elements for hydrogen fuel cell |
| JP2008047392A (en) * | 2006-08-14 | 2008-02-28 | Japan Aerospace Exploration Agency | Fuel cell system |
| KR20090007013A (en) * | 2007-07-13 | 2009-01-16 | 현대자동차주식회사 | Ventilation device of fuel cell vehicle |
| EP2706608A1 (en) * | 2012-09-11 | 2014-03-12 | Neos Alternatives Inc | Fuel and electrical power generating unit |
| WO2014155799A1 (en) * | 2013-03-29 | 2014-10-02 | 日産自動車株式会社 | Liquid-injection-type air cell |
| KR20150067485A (en) * | 2013-12-10 | 2015-06-18 | 주식회사 엘지화학 | Battery/fuel cell hybrid system and its operating method |
| KR102395777B1 (en) | 2015-06-17 | 2022-05-09 | 삼성전자주식회사 | Metal air battery having air supply module and operation method of the metal air battery |
| CN111477918A (en) * | 2020-05-13 | 2020-07-31 | 郑州佛光发电设备有限公司 | Aluminum-air power supply system |
| US12308501B2 (en) * | 2021-06-08 | 2025-05-20 | Hydrogenics Corporation | Venting of sealed fuel cell enclosure |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2106977A5 (en) * | 1970-09-30 | 1972-05-05 | Alsthom | |
| DE3239396C2 (en) * | 1982-10-25 | 1985-01-17 | Accumulatorenwerke Hoppecke Carl Zoellner & Sohn GmbH & Co KG, 5790 Brilon | battery |
| JPH0610988B2 (en) * | 1985-11-20 | 1994-02-09 | 三菱電機株式会社 | Electrolyte replenishing device for stacked fuel cell |
| CA1276972C (en) * | 1986-10-22 | 1990-11-27 | David S. Strong | Multi-cell metal/air battery |
| US4950561A (en) * | 1989-06-29 | 1990-08-21 | Eltech Systems Corporation | Metal-air battery with easily removable anodes |
| US4994332A (en) * | 1989-07-11 | 1991-02-19 | Eltech Systems Corporation | Metal hydroxide crystallizer and filter |
-
1991
- 1991-10-09 US US07/773,511 patent/US5156925A/en not_active Expired - Lifetime
-
1992
- 1992-09-29 WO PCT/CA1992/000429 patent/WO1993007652A1/en not_active Ceased
- 1992-09-29 CA CA002120775A patent/CA2120775C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5156925A (en) | 1992-10-20 |
| CA2120775A1 (en) | 1993-04-15 |
| WO1993007652A1 (en) | 1993-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2120775C (en) | Hydrogen removal system for metal/air fuel cell | |
| EP0311275B1 (en) | Metal/air battery with recirculating electrolyte | |
| CA1315840C (en) | Metal/air battery with seeded recirculating electrolyte | |
| US7201782B2 (en) | Gas generation system | |
| CN100364161C (en) | Fuel cell fill recuperators, fuel cell systems and regenerators for fuel cell fill recuperators | |
| US6849356B2 (en) | Separated flow liquid catholyte aluminum hydrogen peroxide seawater semi fuel cell | |
| US10283789B2 (en) | Fuel cell stack | |
| US5147736A (en) | Metal/air fuel cell with electrolyte flow equalization manifold | |
| CA2422388A1 (en) | Fuel cell arrangement and method for operating a fuel cell arrangement | |
| EP0280764A2 (en) | Efficient electrical power generation system | |
| EP0047792B1 (en) | Battery, gas depolarized electrochemical cell and bipolar element for the battery | |
| CN115976560A (en) | Metal/carbon dioxide battery and hydrogen production and carbon dioxide storage system comprising same | |
| JP2016051521A (en) | Fuel cell system | |
| US5114802A (en) | Caustic-based metal battery with seeded recirculating electrolyte | |
| US20040053085A1 (en) | Hydrogen management system for a fuel cell | |
| JPH0244764B2 (en) | DENKIKAGAKUTEKISANSOBUNRISOCHINOSADOHOHO | |
| CN222770976U (en) | Electrochemical oxygen generator | |
| CN119422272A (en) | Electrochemical cells with electrolyte management | |
| KR830002523B1 (en) | battery | |
| JPH0785899A (en) | Stacked battery | |
| KR20230165923A (en) | Sheet shaped anode feeding style metal-carbon dioxide battery and hydrogen generating and carbon dioxide storage system comprising the same | |
| JPH07105990A (en) | Metal air battery | |
| CN119627313A (en) | Charging unit for flow-type metal-air battery | |
| CN119627312A (en) | Charging unit for mobile metal-air battery | |
| HU184812B (en) | Battery with changable consumable anode, electrochemical cell de polarizable by gas and bipolar cell for the battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |