WO1988001103A1 - Accumulateurs a electrolyte alcalin aqueux - Google Patents

Accumulateurs a electrolyte alcalin aqueux Download PDF

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Publication number
WO1988001103A1
WO1988001103A1 PCT/GB1987/000544 GB8700544W WO8801103A1 WO 1988001103 A1 WO1988001103 A1 WO 1988001103A1 GB 8700544 W GB8700544 W GB 8700544W WO 8801103 A1 WO8801103 A1 WO 8801103A1
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WO
WIPO (PCT)
Prior art keywords
battery
electrolyte
aluminium
metal
electrolytes
Prior art date
Application number
PCT/GB1987/000544
Other languages
English (en)
Inventor
Alfred Chan Chung Tseung
Robert Lovejoy Quarshie
Zu Geng Lin
Original Assignee
The City University
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 City University filed Critical The City University
Publication of WO1988001103A1 publication Critical patent/WO1988001103A1/fr

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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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/045—Cells with aqueous electrolyte characterised by aqueous electrolyte
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • 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
    • H01M12/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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
    • 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

Definitions

  • Batteries having an aqueous alkaline electrolyte This invention relates to batteries having an aqueous alkaline electrolyte, more especially to metal- air batteries, and above all to aluminium-air batteries
  • Aluminium-air battery systems are of two distinct types, namely those in which the aqueous electrolyte comprises a solution of a neutral chloride (such as sodium chloride, potassium chloride or ammonium chloride) and those in which an aqueous alkaline electrolyte is used.
  • a neutral chloride such as sodium chloride, potassium chloride or ammonium chloride
  • an aqueous alkaline electrolyte is used.
  • the alkaline system provides both high specific energy and power density, whereas the saline system, whilst still having reasonably high specific energy density, has much lower power density.
  • An air electrode requires a highly alkaline (or acidic) electrolyte in order to achieve high current densities, and highly acidic electrolytes are unacceptably corrosive towards the aluminium anode and other cell materials.
  • the active anode material is dissolved by the electrolyte, and a build-up of electrical resistance occurs within the electrolyte owing to the accumulation of the resulting reaction products, for example, in the case of an aluminium-air battery with a sodium hydroxide electrolyte, progressive dissolution of the aluminium anode leads to the formation of a highly insoluble sludge comprising precipitated sodium-aluminium hydroxide, which in turn leads to increased cell resistance, reduced performance and cloaking of the electrodes.
  • the present invention provides a metal-air battery, more especially an aluminium-air battery, in which the electrolyte comprises an aqueous mixture of sodium hydroxide and potassium hydroxide.
  • a mixed electrolyte according to the invention is in principle applicable to other metal-air battery systems such as iron-air, cobalt-air and zinc-air, but an especially important application of the invention is in aluminium-air systems, and the invention will accordingly be described hereinafter with particular reference to such systems.
  • a mixed electrolyte according to the invention is in principle also applicable quite generally to batteries having aqueous alkaline electrolytes.
  • batteries include: metal/alkali/MnO 2 (for instance zinc/alkali/MnO 2 ) cadmium, cobalt or iron/alkali/NiO(OH) metal/alkali/silver oxide, where the metal is, for example, magnesium, aluminium, iron, cobalt or zinc.
  • a mixed electrolyte according to the invention greatly alleviates the problems caused by sludge formation without any unacceptable deterioration in conductivity.
  • the battery can be operated for a significantly longer period before the onset of sludge formation and the precipitate that does form tends to agglomerate to form large granules which are relatively easy to flush or clean away.
  • mixed electrolytes according to the invention are equal volume mixtures of the following, all percentages being on a weight/volume basis:
  • Test tubes containing the electrolytes were immersed in a heated water bath to maintain a constant working temperature (25°C). Pieces of an aluminium alloy designated Q4 were then dissolved in each electrolyte until electrolyte saturation. The test tubes were cork-sealed to prevent carbon dioxide absorption. On attaining saturation, the solutions were left to stand, at the constant temperature, for at least 24 hours to allow all undissolved particulate matter to settle down. Aliquot samples of the clear saturated solutions were pipetted into graduated flasks.
  • the samples were then diluted by sufficient factors to enable absorbance readings to be taken, within the linearity range for aluminium, using an Atomic Absorption spectrophotometer. Each electrolyte sample was prepared in duplicate. The Atomic Absorption spectrophotometric method was then used to determine the amount of aluminium dissolved in each saturated electrolyte. The average of the concentrations given by the two samples prepared for each electrolyte was then used to obtain the solubility of the aluminium part of the aluminate/Al(OH) 3 formed during the reaction.
  • Figs. 2 to 4 compare the solubility of aluminium in each electrolyte mixture with the solubilities given by the corresponding solutions of the individual hydroxides.
  • Fig. 2 shows an increase in solubility on mixing equal volumes of 30 % NaOH and 50 % KOH. A gain of about 75 % in solubility is achieved as compared with 30 % NaOH and about 62 % as compared with 50 % KOH. In Fig. 3, a remarkable increase in solubility is shown. There is an immense gain of about 140 % in solubility for 30 % KOH on mixing with 50 % NaOH; there is about 58 % gain for 50 % NaOH.
  • Fig. 4 shows only a slight increase in solubility on mixing equal volumes of 50 % NaOH and 50 % KOH. This could be due to the fact that too many ions already exist in solution, with the result that the solution has almost reached its saturation point even before the introduction of the aluminium ions.
  • Fig. 5 compares the solubility value given by electrolyte No. 10 (50 % NaOH and 30 % KOH) with the solubilities given by the solution concentrations conventionally used as electrolytes for aluminium-air batteries and also with the concentrations of individual hydroxides at which our experiments have shown that very high solubility values are obtained.
  • a very large gain of 140 % in solubility is found as compared with 30 % KOH.
  • electrolytes (2) and (3) which gave the best results in the solubility experiments, were investigated for other relevant electrolyte properties.
  • Tests were carried out on electrolytes (2) and (3) to determine the following: (i) The polarisation characteristics of aluminium in the electrolytes; (ii) The anodic efficiency of aluminium in the electrolytes; (iii) The self-discharge characteristics of aluminium in the electrolytes; (iv) The conductivity of the electrolytes; (v) The pH of the electrolytes; (vi) The viscosity of the electrolytes; and (vii) The nature of the reaction products formed on dissolution of aluminium in the electrolytes was examined using Scanning Electron Microscopy (SEM) and X-ray fluorescence and diffraction techniques. In order to provide a basis for comparison, the same tests were carried out on conventional single hydroxide electrolytes, 30 % (w/v) NaOH and 30 % (w/v) KOH.
  • SEM Scanning Electron Microscopy
  • the concentration of each hydroxide in a mixed electrolyte according to the invention will in general be at least 2 % (w/v), and usually at least 5 %.
  • the concentration of sodium hydroxide in a mixed electrolyte according to the invention is advantageously in the range of from 10 to 70 % (w/v), preferably in the range of from 20 to 60 %, and is more especially in the range of from 30 to 50 %.
  • the concentration of potassium hydroxide in a mixed electrolyte according to the invention is advantageously in the range of from 10 to 80 % (w/v), preferably in the range of from 30 to 60 %, and is more especially in the range of from 30 to 50 %.
  • the ratio of NaOH to KOH by volume may be in the range of from 2:1 to 1:1 preferably in the range of from 1.5:1 to 1:1, and is more especially approximately 1:1.
  • a battery according to the invention may be advantageous in some cases to operate a battery according to the invention initially with an electrolyte comprising only one of the hydroxides (for example, potassium hydroxide) and then to add the other hydroxide after a period of operation.
  • an electrolyte comprising only one of the hydroxides (for example, potassium hydroxide) and then to add the other hydroxide after a period of operation.
  • Such a procedure can offset, at least to some extent, what might otherwise be an increased start-up time in those instances where the over-voltage is higher at room temperature with a mixed electrolyte according to the invention.
  • an aluminium-air battery according to the invention is operated at an internal temperature in the range of from 40 to 45°C.
  • the battery can be used in environments at temperatures as low as -20°C and in such environments it will self-heat to an adequate working temperature.
  • a further problem encountered in the operation of aluminium-air batteries is that, when aluminium alloy anodes are in contact with aqueous electrolytes, parasitic reaction occurs leading to the release of hydrogen which in turn presents explosion hazards.
  • a mixed electrolyte according to the invention includes a hydrogen evolution inhibitor.
  • the inhibitor is dissolved mercury (as HgO) in an amount up to that which gives a saturated solution.
  • HgO may be intorduced by incorporating HgCl 2 with the electrolyte whilst stirring at room temperature.
  • the presence of HgO in solution in the electrolyte acts as an effective hydrogen evolution inhibitor without causing undesirable passivation of aluminium alloy anodes.
  • the HgO content in solution in the electrolyte will be in the range of from 1 to 2 ppb, more especially about 1.5 ppb. it is remarkable that such a small amount of dissolved mercury can give such useful results.
  • HgO as a hydrogen evolution inhibitor is found to be greater at higher temperatures (for example, 40oC) than at room temperature (25oC). Even at lower temperature, however, the total working surface area of a typical aluminium electrode is such that even a marginal improvement in hydrogen evolution inhibition is worhtwhile.
  • hydrogen evolution inhibitors which may be used are, for example, K 2 Cr 2 O 7 , Na 2 S, Na 2 O : SiO 2 solution, or dissolved gallium.
  • a hydrogen/oxygen recombination device can be used to eliminate, or at least reduce, any remaining evolved hydrogen.
  • the or each aluminium anode in an aluminium-air battery according to the invention comprises an alloy of aluminium with one or more of Zn, Ga, In, Pb, bi and Sn.
  • Such alloying with elements of high hydrogen over-potential has the effect of destabilising the passivating oxide film on the surface of pure aluminium without at the same time increasing the rate of corrosion.
  • An Al-Zn alloy has been found to have relatively little self-discharge, but tends to passivate at high current densities.
  • the addition of Ga or In to the Al-Zn alloy has been found to improve its anodic performance. The performance is subbued, however, if the concentration of Zn in the alloy is high (say, > 4 %). Thus, even though Zn is extremely valuable in improving the electrode properties of aluminium, the amount of Zn added must be closely controlled.
  • the alloy designated Q4 performs very well at high current densities with a high utilisation, but is also found to have a rather high self-discharge with the evolution of a relatively large amount of hydrogen. This may be attributed to the comparatively high concentration of Fe present in the Q4 alloy. Thus, to reduce the rate of self-discharge, the concentration of Fe must be kept to a minimum. Similar considerations apply to Cu.
  • the alloy designated Q4 has proved to be the best of all those we have tested.
  • the problem of self-discharge, which results in loss of capacity under standby conditions, can be avoided to a certain extent by withdrawing the electrolyte from the cell, automatically, whenever power is not required and returning it to the cell when needed. Also, as hereinbefore described, measures can be taken to restrict the extent of parasitic hydrogen evolution and/or to cause recombination with oxygen.
  • a foamy white gel comprising aluminium chloride
  • the air (or oxygen) electrode may be of any conventional form.
  • such electrodes typically comprise a porous, conducting solid, for example, graphite, into which both the electrolyte and the gas can penetrate.
  • wet-proofing some of the pores, the contact angle is raised, and electrolyte cannot penetrate.
  • Such wet-proofing may be effected, for example, by polytetrafluoroethylene (PTFE) or by paraffin wax.
  • PTFE polytetrafluoroethylene
  • paraffin wax paraffin wax
  • a wet-proof technique may be used.
  • the oxygen side of the electrode may be cladded with a thin layer of a porous water-repellent plastics material, such as a mixture of PTFE and acetylene black.
  • each or at least one electrode incorporates an electrocatalyst such as, for example, nickel cobalt oxide (NiCo 2 O 4 ) or, preferably, lithiated cobalto-cobaltic oxide (Li/Co 3 O 4 ).
  • electrocatalysts are known per se and may be used in a customary manner. Thus, for example they may be applied as powders, optionally in admixture with one or more other suitable electrocatalysts, in polymeric dispersion (for example, polytetrafluoroethylene dispersion) to supports (for example, nickel screens) which are dried and then cured to form polymer-bonded electrodes.
  • the anode may be of any customary form, but it is an important advantage of the use of mixed electrolytes according to the invention that it is possible to construct the anode in the form of a plurality of small discrete bodies accommodated in a conducting basket formed, for example, of stainless steel mesh (e.g. 18 Cr/2 Mo ferritic steel) . With such an arrangement , it is possible to have automatic feeding of aluminium to the cell over long periods. Such an anode construction would not be practicable with a conventional single-hydroxide electrolyte, because the substantially more rapid sludge formation observed with such electrolytes would tend to isolate adjacent spheres electrically from one another.
  • the discrete bodies may be of any form that is capable of being fed freely from a hopper, but are preferably small spheres. Preferably, the diameter of the spheres is in the range of from 3 to 5 mm.
  • a battery according to the invention can be used to provide power for applications both onshore and offshore. It can be used as the main power source in submersibles, life-boats, military field equipment and reconnaissance vehicles. It can also be used as an emergency power source for lighting, and for burglar and fire alarms, computer memory banks, as starters for car engines and as backups for generators.
  • An aqueous electrolyte for use according to the invention may be in any suitable physical form, for example, in a liquid or gel form or supported in a porous medium.
  • battery is used herein to include arrangements comprising only a single cell as well as arrangements comprising more than one cell.
  • FIG. 8 is a schematic perspective view, partly in section, in which the reference numerals have the following meanings: 1 positive terminal
  • the anode/cathode separation was 2.3 mm and the cathode incorporated an Li/Co 3 O 4 electrocatalyst.
  • the electrolyte was an equal volume mixture of 30 % w/v KOH and 50 % w/v NaoH saturated with HgO (1.5 ppb).
  • the cell can be recharged, by putting in more aluminium and fresh electrolyte, to operate over any length of time.
  • the energy density of the cell calculated for a 24 hour operation time, was nearly 400 Wh/Kg; 3,714 Wh/Kg for the Al anode.
  • the cell can be operated from as low as -20°C without the use of an external heater to warm it up.

Abstract

Un électrolyte pour accumulateurs, plus particulièrement pour accumulateurs métal-air, comprend un mélange aqueux d'hydroxyde de sodium et d'hydroxyde de potassium. L'emploi d'un tel électrolyte permet de limiter les problèmes de formation de boue tout en maintenant une bonne conductivité ainsi que d'autres propriétés.
PCT/GB1987/000544 1986-08-01 1987-07-30 Accumulateurs a electrolyte alcalin aqueux WO1988001103A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB08618833A GB2195201A (en) 1986-08-01 1986-08-01 Batteries having an aqueous alkaline electrolyte
GB8618833 1986-08-01

Publications (1)

Publication Number Publication Date
WO1988001103A1 true WO1988001103A1 (fr) 1988-02-11

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PCT/GB1987/000544 WO1988001103A1 (fr) 1986-08-01 1987-07-30 Accumulateurs a electrolyte alcalin aqueux

Country Status (5)

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EP (1) EP0316336A1 (fr)
JP (1) JPH02500313A (fr)
AU (1) AU7782787A (fr)
GB (1) GB2195201A (fr)
WO (1) WO1988001103A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358335A1 (fr) * 1988-08-09 1990-03-14 Alcan International Limited Batteries à électrodes en aluminium
CN105140596A (zh) * 2015-09-06 2015-12-09 河南科技大学 一种空气电池用铝合金阳极材料、制备方法及铝空气电池
US9680193B2 (en) 2011-12-14 2017-06-13 Eos Energy Storage, Llc Electrically rechargeable, metal anode cell and battery systems and methods

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413881A (en) * 1993-01-04 1995-05-09 Clark University Aluminum and sulfur electrochemical batteries and cells
JP2013243108A (ja) * 2012-04-23 2013-12-05 Sharp Corp 金属空気電池およびエネルギーシステム
JP6149404B2 (ja) * 2013-01-21 2017-06-21 日産自動車株式会社 アルミニウム−空気電池

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DE1804096A1 (de) * 1967-10-30 1969-05-14 Texas Instruments Inc Elektrolyt fuer Nickel-Kadmium-Akkumulatoren
US3850693A (en) * 1972-10-26 1974-11-26 Union Carbide Corp Corrosion inhibitor for alkaline aluminum cells
US4198475A (en) * 1977-10-17 1980-04-15 Reynolds Metals Company Methods and apparatus for generating heat and electrical energy from aluminum
JPH0674358A (ja) * 1992-08-25 1994-03-15 Mitsubishi Electric Corp 流体制御バルブ

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US3553027A (en) * 1968-02-02 1971-01-05 Leesona Corp Electrochemical cell with lead-containing electrolyte and method of generating electricity
GB1437746A (en) * 1973-08-01 1976-06-03 Accumulateurs Fixes Air depolarized electric cell
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DE2819685C3 (de) * 1978-05-05 1981-10-15 Silberkraft-Leichtakkumulatoren Gmbh, 4100 Duisburg Elektrolyt für eine galvanische Primärzelle mit wenigstens einer negativen Elektrode aus Aluminium oder einer Aluminiumlegierung
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Publication number Priority date Publication date Assignee Title
DE1804096A1 (de) * 1967-10-30 1969-05-14 Texas Instruments Inc Elektrolyt fuer Nickel-Kadmium-Akkumulatoren
US3850693A (en) * 1972-10-26 1974-11-26 Union Carbide Corp Corrosion inhibitor for alkaline aluminum cells
US4198475A (en) * 1977-10-17 1980-04-15 Reynolds Metals Company Methods and apparatus for generating heat and electrical energy from aluminum
JPH0674358A (ja) * 1992-08-25 1994-03-15 Mitsubishi Electric Corp 流体制御バルブ

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CHEMICAL ABSTRACTS, Volume 87, 1977, (Columbus, Ohio, US), see page 183, Abstract 87828u, & JP, A, 7741840 (Furukawa Battery Co., Ltd) 31 March 1977 *
PATENT ABSTRACTS OF JAPAN, Volume 9, No. 212 (E-339) (1935), 29 August 1985, seee the whole Abstract & JP, A, 6074358 (Hitachi Maxell K.K.) 26 April 1985 *
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358335A1 (fr) * 1988-08-09 1990-03-14 Alcan International Limited Batteries à électrodes en aluminium
US9680193B2 (en) 2011-12-14 2017-06-13 Eos Energy Storage, Llc Electrically rechargeable, metal anode cell and battery systems and methods
EP2792004B1 (fr) * 2011-12-14 2017-11-08 Eos Energy Storage, LLC Élément électriquement rechargeable à anode métallique, ainsi que systèmes et procédés d'accumulateurs correspondants
CN105140596A (zh) * 2015-09-06 2015-12-09 河南科技大学 一种空气电池用铝合金阳极材料、制备方法及铝空气电池
CN105140596B (zh) * 2015-09-06 2018-02-13 河南科技大学 一种空气电池用铝合金阳极材料、制备方法及铝空气电池

Also Published As

Publication number Publication date
GB2195201A (en) 1988-03-30
JPH02500313A (ja) 1990-02-01
AU7782787A (en) 1988-02-24
EP0316336A1 (fr) 1989-05-24
GB8618833D0 (en) 1986-09-10

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