WO1999060654A1 - Metal/oxygen battery or fuel cell with oxygen cathode containing oxygen concentrator and regulating means of controlling its supply - Google Patents

Metal/oxygen battery or fuel cell with oxygen cathode containing oxygen concentrator and regulating means of controlling its supply Download PDF

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Publication number
WO1999060654A1
WO1999060654A1 PCT/US1999/010972 US9910972W WO9960654A1 WO 1999060654 A1 WO1999060654 A1 WO 1999060654A1 US 9910972 W US9910972 W US 9910972W WO 9960654 A1 WO9960654 A1 WO 9960654A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxygen
concentrator
metal
cell according
cathode
Prior art date
Application number
PCT/US1999/010972
Other languages
French (fr)
Inventor
Vladimir Gartstein
James Berger Camden
Original Assignee
The Procter & Gamble Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP99923196A priority Critical patent/EP1078412A1/en
Priority to AU40022/99A priority patent/AU4002299A/en
Priority to JP2000550173A priority patent/JP2002516474A/en
Publication of WO1999060654A1 publication Critical patent/WO1999060654A1/en

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Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates generally to the use of an oxygen concentrator to supply fairly high purity oxygen under pressure to a zinc/oxygen battery.
  • the oxygen is supplied in a controlled manner.
  • Metal-air batteries utilize multiple electrochemical cells. Each cell is comprised of an air permeable cathode, a metallic anode, and an aqueous electrolyte. Because they use oxygen from air as a reactant in the electrochemical reaction rather than a heavier material, metal-air batteries have a relatively high-energy density. During discharge of the zinc-air cell, oxygen from ambient air is converted at the cathode to hydroxide ions, zinc is oxidized at the anode through a reaction with the hydroxide ions, and electrons are released to provide energy.
  • One of the problems with the zinc-air battery is gating or valving the oxygen into the battery. You need to shut off the oxygen when the battery is not under load and then match the oxygen flow rate to the load during use.
  • the second problem is controlling the water inside the battery.
  • the third is dispersing the oxygen over the cathode area inside the battery for the efficient oxidation of all of the zinc.
  • the present invention provides a better solution to solving the problem of providing oxygen in a metal-air battery.
  • the combination of the oxygen concentrator in a zinc/oxygen battery wherein the oxygen is supplied in a controllable and controlled manner is disclosed.
  • Figure 1 is a diagram of the oxygen concentrator in a battery.
  • Metal-air batteries contain an anode which is made from metals that can be oxidized during discharge in a metal-oxygen cell to produce electrical energy.
  • metals include lead, zinc, lithium, iron, cadmium, aluminum, and magnesium.
  • Zinc is normally preferred because of its availability, energy density, safety, and relatively low cost.
  • An electrolyte is also provided.
  • an aqueous electrolyte solution of the Group I metal hydroxides is used. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, or the like.
  • Metal-air batteries have an air permeable cathode.
  • This invention utilizes an oxygen concentrator instead of air as the reactant. Since air only contains about 20% oxygen, a greater flow of air is required to provide the required oxygen for the cathode. Concentrating the oxygen to the air permeable cathode simplifies the battery design.
  • a rotary compressor (1 ), driven by a battery or air flow past a moving vehicle is used to create pressurized air.
  • a variable compressor controlled by a feedback loop can also be used.
  • the air can be passed over water to humidify it.
  • This humidifier (3) can be placed before or after the oxygen concentrator (5), but preferably after the oxygen concentrator.
  • the compressed air passed through an oxygen concentrator which contains molecular sieves or membranes which allow >95% of the oxygen to pass through and the nitrogen is vented.
  • the oxygen that is concentrated contains a small amount of carbon dioxide, nitrogen, and water and is referred to as "high purity oxygen.”
  • Preferred oxygen concentrators use zeolite molecular sieve or absorbent material. Activated carbon molecular sieve to absorb the argon can also be used in combination with the zeolite.
  • the carbon dioxide in the oxygen stream exiting the oxygen concentrator can be absorbed by a small cartridge (7) of absorbent material such as calcium oxide or lithium hydroxide.
  • the oxygen can be humidified (9) either as it exits the cartridge or prior to the concentration apparatus. In very arid climates, a water reservoir is used (11 ).
  • Humidifier valves (13) which are controlled by a water sensor (19) in the battery can be used to control the amount of water entering the battery (15).
  • An oxygen flow rate valve (17) is used to control the amount of oxygen entering the battery.
  • the control of the flow rate of the oxygen to the battery matches the load of the battery (23).
  • the pressurized oxygen flow also insures complete mixing or dispersion of oxygen throughout oxygen electrode.
  • a pressure relief value is used to vent the remaining gas and water to the atmosphere (25).
  • This battery contains a pressure release valve to release the nitrogen and water to the air.
  • the nitrogen is desorbed form the zeolite by a regenerative purge flow or through the use of two zeolite beds.
  • one bed or pair of beds receives a high pressure air as feed gas which pressurizes the beds and establishes oxygen flow.
  • the high pressure gas in the other beds is vented to a lower pressure and this depressurization serves to desorb the nitrogen and argon previously adsorbed during the high pressure phase of the cycle (see, US 4,880,443 issued in 1989).
  • the oxygen inlet of the air manager system is set initially to a predetermined position based upon the status of the load to control the amount of oxygen supplied to the cell.
  • the direction of the oxygen flow may be changed by a plurality of baffles (21) incorporated into the pathway of the oxygen.
  • the baffles used for changing the direction of the flow of the oxygen define a serpentine path across the surface of the cathode covering essentially all points of the surface.
  • the cathode has an inlet and outlet and a plurality of baffles to define a torturous path for the oxygen to flow from inlet to outlet.
  • a catalytic element can be placed in the path of the oxygen flow for catalyzing the recombination of the hydrogen and oxygen gas generated by a rechargeable metal oxygen battery.
  • This same oxygen concentrator technology can be applied to a fuel cell which uses hydrogen as the anode.
  • the oxygen concentrator provides a more efficient source of oxygen for these cells. Carbon monoxide in the air can poison the fuel cell. Using the oxygen concentrator to purify the source of oxygen can prevent or limit this interference by carbon monoxide and other impurities in the air.

Abstract

The present invention relates generally to the use of an oxygen concentrator to supply fairly high purity oxygen under pressure to a zinc/oxygen battery. The oxygen is supplied in a controlled manner.

Description

METAL/OXYGEN BATTERY OR FUEL CELL WITH OXYGEN CATHODE CONTAINING OXYGEN CONCENTRATOR AND REGULATING MEANS OF CONTROLLING ITS SUPPLY
Technical Field
The present invention relates generally to the use of an oxygen concentrator to supply fairly high purity oxygen under pressure to a zinc/oxygen battery. The oxygen is supplied in a controlled manner.
Background Of The Invention
Metal-air batteries utilize multiple electrochemical cells. Each cell is comprised of an air permeable cathode, a metallic anode, and an aqueous electrolyte. Because they use oxygen from air as a reactant in the electrochemical reaction rather than a heavier material, metal-air batteries have a relatively high-energy density. During discharge of the zinc-air cell, oxygen from ambient air is converted at the cathode to hydroxide ions, zinc is oxidized at the anode through a reaction with the hydroxide ions, and electrons are released to provide energy.
One of the problems with the zinc-air battery is gating or valving the oxygen into the battery. You need to shut off the oxygen when the battery is not under load and then match the oxygen flow rate to the load during use. The second problem is controlling the water inside the battery. And the third is dispersing the oxygen over the cathode area inside the battery for the efficient oxidation of all of the zinc.
One solution to these problems is supplying the battery with pressurized air. The difficulty of this system resides in the management of the humidity and temperature within the battery given the large volumes of air flowing through the battery to supply the oxygen.
It is an object of this invention to solve the air flow problem by using an oxygen concentrator to supply fairly high purity oxygen under pressure to the zinc oxygen battery in a controlled manner. This and other objects of the invention will become obvious as described herein. Summary Of The Invention
The present invention provides a better solution to solving the problem of providing oxygen in a metal-air battery. The combination of the oxygen concentrator in a zinc/oxygen battery wherein the oxygen is supplied in a controllable and controlled manner is disclosed.
Description Of The Figure
Figure 1 is a diagram of the oxygen concentrator in a battery.
Detailed Description Of The Invention
Metal-air batteries contain an anode which is made from metals that can be oxidized during discharge in a metal-oxygen cell to produce electrical energy. Such metals include lead, zinc, lithium, iron, cadmium, aluminum, and magnesium. Zinc is normally preferred because of its availability, energy density, safety, and relatively low cost. An electrolyte is also provided. Generally, an aqueous electrolyte solution of the Group I metal hydroxides is used. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, or the like.
Metal-air batteries have an air permeable cathode.
This invention utilizes an oxygen concentrator instead of air as the reactant. Since air only contains about 20% oxygen, a greater flow of air is required to provide the required oxygen for the cathode. Concentrating the oxygen to the air permeable cathode simplifies the battery design.
A rotary compressor (1 ), driven by a battery or air flow past a moving vehicle is used to create pressurized air. A variable compressor controlled by a feedback loop can also be used. Optionally, the air can be passed over water to humidify it. This humidifier (3) can be placed before or after the oxygen concentrator (5), but preferably after the oxygen concentrator. The compressed air passed through an oxygen concentrator which contains molecular sieves or membranes which allow >95% of the oxygen to pass through and the nitrogen is vented. The oxygen that is concentrated contains a small amount of carbon dioxide, nitrogen, and water and is referred to as "high purity oxygen."
Preferred oxygen concentrators use zeolite molecular sieve or absorbent material. Activated carbon molecular sieve to absorb the argon can also be used in combination with the zeolite. The carbon dioxide in the oxygen stream exiting the oxygen concentrator can be absorbed by a small cartridge (7) of absorbent material such as calcium oxide or lithium hydroxide. The oxygen can be humidified (9) either as it exits the cartridge or prior to the concentration apparatus. In very arid climates, a water reservoir is used (11 ). Humidifier valves (13) which are controlled by a water sensor (19) in the battery can be used to control the amount of water entering the battery (15). An oxygen flow rate valve (17) is used to control the amount of oxygen entering the battery.
The control of the flow rate of the oxygen to the battery matches the load of the battery (23). The pressurized oxygen flow also insures complete mixing or dispersion of oxygen throughout oxygen electrode. A pressure relief value is used to vent the remaining gas and water to the atmosphere (25).
This battery contains a pressure release valve to release the nitrogen and water to the air. The nitrogen is desorbed form the zeolite by a regenerative purge flow or through the use of two zeolite beds. In a two step cycle, one bed or pair of beds (one zeolite and one carbon) receives a high pressure air as feed gas which pressurizes the beds and establishes oxygen flow. Simultaneously the high pressure gas in the other beds is vented to a lower pressure and this depressurization serves to desorb the nitrogen and argon previously adsorbed during the high pressure phase of the cycle (see, US 4,880,443 issued in 1989).
While the use of the oxygen concentrator in large batteries for electrical vehicles is preferred, there are smaller oxygen concentrators which could be used to make smaller batteries. The oxygen inlet of the air manager system is set initially to a predetermined position based upon the status of the load to control the amount of oxygen supplied to the cell.
In order to ensure that the oxygen flow reacts with the entire surface of the cathode, the direction of the oxygen flow may be changed by a plurality of baffles (21) incorporated into the pathway of the oxygen. The baffles used for changing the direction of the flow of the oxygen define a serpentine path across the surface of the cathode covering essentially all points of the surface. Preferably, the cathode has an inlet and outlet and a plurality of baffles to define a torturous path for the oxygen to flow from inlet to outlet.
A catalytic element can be placed in the path of the oxygen flow for catalyzing the recombination of the hydrogen and oxygen gas generated by a rechargeable metal oxygen battery.
This same oxygen concentrator technology can be applied to a fuel cell which uses hydrogen as the anode. The oxygen concentrator provides a more efficient source of oxygen for these cells. Carbon monoxide in the air can poison the fuel cell. Using the oxygen concentrator to purify the source of oxygen can prevent or limit this interference by carbon monoxide and other impurities in the air.

Claims

What is claimed is:
1. A metal-oxygen cell having an oxygen cathode, a metal anode and an electrolyte, said cell characterized in that it comprises a means for concentrating oxygen to supply high-purity oxygen to the cathode and a means for controlling oxygen entering the cathode comprising a current monitoring circuit connected to measure an output current drawn from the metal/oxygen cell by a load during operation, and an oxygen control circuit responsive to said current drawn to open said means for admitting oxygen from the concentrator for a predetermined time.
2. A cell according to Claim 1 , wherein said oxygen concentrator contains zeolite molecular seives.
3. A cell according to Claim 1 or 2, wherein said oxygen concentrator comprises two zeolite beds, one of which is regenerated by lowering the pressure in it.
4. A cell according to any of Claims 1- 3, wherein said oxygen concentrator contains an absorbent carbon bed.
5. A cell according to any of Claims 1- 4, wherein said metal anode is zinc.
6. A cell according to any of Claims 1- 5, wherein said electrolyte is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide.
7. A fuel cell having an oxygen cathode, a hydrogen anode, and an electrolyte, said cell characterized in that it comprises a means for oxygen entering the cathode comprising a current monitoring circuit connected to measure an output current drawn from the metal/oxygen cell by a load during operation, and an oxygen control circuit responsive to said current drawn to open said means for admitting oxygen from the concentrator for a predetermined time.
8. A fuel cell according to Claim 7, wherein said oxygen concentrator contains zeolite molecular seives.
9. A fuel cell according to Claim 7 or 8, wherein said oxygen concentrator comprises two zeolite beds, one of which is regenerated by lowering the pressure in it.
10. A fuel cell according to any of Claims 7-9, wherein said oxygen concentrator contains an absorbent carbon bed.
PCT/US1999/010972 1998-05-18 1999-05-18 Metal/oxygen battery or fuel cell with oxygen cathode containing oxygen concentrator and regulating means of controlling its supply WO1999060654A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP99923196A EP1078412A1 (en) 1998-05-18 1999-05-18 Metal/oxygen battery or fuel cell with oxygen cathode containing oxygen concentrator and regulating means of controlling its supply
AU40022/99A AU4002299A (en) 1998-05-18 1999-05-18 Metal/oxygen battery or fuel cell with oxygen cathode containing oxygen concentrator and regulating means of controlling its supply
JP2000550173A JP2002516474A (en) 1998-05-18 1999-05-18 Metal / oxygen battery or fuel cell with oxygen cathode including oxygen concentrator and control means for controlling its supply

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8579898P 1998-05-18 1998-05-18
US60/085,798 1998-05-18

Publications (1)

Publication Number Publication Date
WO1999060654A1 true WO1999060654A1 (en) 1999-11-25

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EP (1) EP1078412A1 (en)
JP (1) JP2002516474A (en)
CN (1) CN1308781A (en)
AR (1) AR013041A1 (en)
AU (1) AU4002299A (en)
CO (1) CO5060451A1 (en)
PE (1) PE20000666A1 (en)
WO (1) WO1999060654A1 (en)

Cited By (13)

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Publication number Priority date Publication date Assignee Title
DE10051664A1 (en) * 2000-10-18 2002-08-08 Xcellsis Gmbh Fuel cell system for a motor vehicle
EP2409355A2 (en) * 2009-03-16 2012-01-25 Eveready Battery Company, Inc. Oxygen-consuming battery with improved high rate capability
US8119295B2 (en) 2010-07-01 2012-02-21 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US8658319B2 (en) 2010-07-01 2014-02-25 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
WO2014135295A1 (en) * 2013-03-04 2014-09-12 Robert Bosch Gmbh Component for oxygen enrichment, component stack, device for obtaining a fluid enriched with oxygen, metal-oxygen battery and motor vehicle
US8968942B2 (en) 2010-07-01 2015-03-03 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US9147920B2 (en) 2010-07-01 2015-09-29 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US9209503B2 (en) 2010-07-01 2015-12-08 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US9362581B2 (en) 2011-10-28 2016-06-07 Ngk Insulators, Ltd. Metal-air battery system including CO2 selective absorber and operating method therefor
CN106356591A (en) * 2015-07-14 2017-01-25 三星电子株式会社 Metal air battery and operation method of the metal air battery
US9821314B2 (en) 2012-09-24 2017-11-21 Cornell University Methods, systems, and applications for solar-thermal microfluidic PCR
US20170365899A1 (en) * 2014-12-18 2017-12-21 John F. Christensen Metal/Air Battery with Gas Separations Unit and Load-Leveling Oxygen Storage System
US10026958B2 (en) 2012-11-06 2018-07-17 Cornell University Carbon dioxide assisted metal-oxygen battery and related method

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JP4967890B2 (en) 2007-05-01 2012-07-04 トヨタ自動車株式会社 Air battery system
JP4434246B2 (en) 2007-07-24 2010-03-17 トヨタ自動車株式会社 Air battery system
JP5353430B2 (en) * 2009-05-14 2013-11-27 トヨタ自動車株式会社 Air battery system
US9166218B2 (en) * 2012-02-24 2015-10-20 Ford Global Technologies, Llc Electrolyte replenishing system and method
DE102014208044A1 (en) * 2014-04-29 2015-10-29 Mahle International Gmbh Metal-air battery
JP6626456B2 (en) * 2014-04-29 2019-12-25 マーレ インターナショナル ゲゼルシャフト ミット ベシュレンクテル ハフツングＭＡＨＬＥ Ｉｎｔｅｒｎａｔｉｏｎａｌ ＧｍｂＨ Air battery
KR102409386B1 (en) 2015-07-08 2022-06-15 삼성전자주식회사 Metal air battery system and method for operating the same
CN109037856A (en) * 2018-08-24 2018-12-18 Cnus技术公司 A kind of power metal-air battery power ascension device

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10051664A1 (en) * 2000-10-18 2002-08-08 Xcellsis Gmbh Fuel cell system for a motor vehicle
EP2409355A4 (en) * 2009-03-16 2013-08-07 Eveready Battery Inc Oxygen-consuming battery with improved high rate capability
EP2409355A2 (en) * 2009-03-16 2012-01-25 Eveready Battery Company, Inc. Oxygen-consuming battery with improved high rate capability
US9209503B2 (en) 2010-07-01 2015-12-08 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US8658319B2 (en) 2010-07-01 2014-02-25 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US9502718B2 (en) 2010-07-01 2016-11-22 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US8968942B2 (en) 2010-07-01 2015-03-03 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US9147920B2 (en) 2010-07-01 2015-09-29 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US8119295B2 (en) 2010-07-01 2012-02-21 Ford Global Technologies, Llc Metal oxygen battery containing oxygen storage materials
US9362581B2 (en) 2011-10-28 2016-06-07 Ngk Insulators, Ltd. Metal-air battery system including CO2 selective absorber and operating method therefor
US9821314B2 (en) 2012-09-24 2017-11-21 Cornell University Methods, systems, and applications for solar-thermal microfluidic PCR
US10026958B2 (en) 2012-11-06 2018-07-17 Cornell University Carbon dioxide assisted metal-oxygen battery and related method
US20160006091A1 (en) * 2013-03-04 2016-01-07 Robert Bosch Gmbh Component for Oxygen Enrichment, Component Stack, Device for Obtaining a Fluid Enriched with Oxygen, Metal-Oxygen Battery and Motor Vehicle
WO2014135295A1 (en) * 2013-03-04 2014-09-12 Robert Bosch Gmbh Component for oxygen enrichment, component stack, device for obtaining a fluid enriched with oxygen, metal-oxygen battery and motor vehicle
US9899713B2 (en) 2013-03-04 2018-02-20 Robert Bosch Gmbh Component for oxygen enrichment, component stack, device for obtaining a fluid enriched with oxygen, metal-oxygen battery and motor vehicle
US20170365899A1 (en) * 2014-12-18 2017-12-21 John F. Christensen Metal/Air Battery with Gas Separations Unit and Load-Leveling Oxygen Storage System
US10741894B2 (en) * 2014-12-18 2020-08-11 Robert Bosch Gmbh Metal/air battery with gas separations unit and load-leveling oxygen storage system
CN106356591A (en) * 2015-07-14 2017-01-25 三星电子株式会社 Metal air battery and operation method of the metal air battery

Also Published As

Publication number Publication date
AR013041A1 (en) 2000-11-22
JP2002516474A (en) 2002-06-04
EP1078412A1 (en) 2001-02-28
CO5060451A1 (en) 2001-07-30
AU4002299A (en) 1999-12-06
PE20000666A1 (en) 2000-08-07
CN1308781A (en) 2001-08-15

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