GB2226692A

GB2226692A - High temperature cell

Info

Publication number: GB2226692A
Application number: GB8928984A
Authority: GB
Inventors: Roger John Wedlake; Peter Barrow; Nigel David Nicholson
Original assignee: Lilliwyte SA
Current assignee: Lilliwyte SA
Priority date: 1988-12-22
Filing date: 1989-12-22
Publication date: 1990-07-04
Anticipated expiration: 2009-12-22
Also published as: GB8928984D0; JPH02215058A; JP3054160B2; GB2226692B; GB8829951D0; ZA899885B; DE3942179A1

Description

1 T- %, Electrochemical Cell THIS INTENTION relates to a method of making

an electrochemical cell. The invention relates also to a precursor for a high temperature electrochemical cell.

According to a first aspect of the invention, there is provided a method of making a precursor for an electrochemical cell of the type comprising an anode compartment containing, at the operating temperature of the cell and when the cell is in its discharged state, a molten alkali metal anode, and a cathode compartment containing, at said operating temperature and in said discharged state, an alkali metal aluminium halide molten salt electrolyte which is also molten at the operating temperature of the cell, and having the fo=la NiAlHal 4' wherein M is the alkali metal of the anode and Hal is a halide, the cathode compartment containing also a cathode which comprises an electronically conductive electrolyte - permeable matrix which has dispersed therein an active cathode substance which includes a transition metal T selected from the group comprising Fe, Ni, Co, Cr, Cu, Yin and mixtures thereof, the matrix being impregnated with said electrolyte, and, separating the anode compartment from the cathode compartment, a separator which comprises a solid conductor of the ions of the alkali metal of the anode or a micromolecular sieve which contains said alkali metal sorbed therein, which method comprises loading into a cathode compartment of a cell housing comprising an anode compartment separated from a cathode compartment by a separator which is a solid conductor of ions of alkali metal M or is a micromolecular sieve which contains alkali metal M sorbed therein, an alkali metal aluminium halide molten salt electrolyte having the formula MAlHal 4 wherein M i s the alkali metal of the separator and Hal is a halide; an alkali metal hali de M Hal wherein M and Hal are respectively the same alkali metal and halide as in the molten salt electrolyte; an active cathode substance which comprises a transition metal T selected from the group comprising Fe, Ni, Co, Cr, Cu, Mn and mixtures thereof; and as an additive, at least one further substance, X, thereby to form an electrochemical cell precursor, with X being capable, when the cell precursor is subjected to charging at a temperature at which the molten salt electrolyte and alkali metal M are molten, of reacting at a voltage lower than the voltage required to charge the cell according to the cathode compartment reaction alHal+T 2M+THal (1) to generate alkali metal in the anode compartment such that, after substantially all the substance X has reacted, a cell in discharged state results, the cell in discharged state being chargeable to cause the active cathode substance to be halogenated, with alkali metal M or further alkali metal M being produced and passing through the separator into the anode compartment, the proportions of alkali metal halide NHal, molten salt electrolyte and additive loaded into the cathode compartment being selected so that when the cell is fully charged and all the available active cathode substance has been halogenated, the proportion of alkali metal ions and aluminium ions in the electrolyte is such that the solubility of the active cathode substance in the molten electrolyte is at or near its minimum, with the provisos that .,t (i) (ii) the additive X is compatible with the molten salt electrolyte, the separator and the active cathode substance; when the substance, X, is an element, it is (a) not A1 or Zn, or a mixture of Al and Zn, and (b) not selected from the d-block transition elements of the periodic table of elements, apart from Group MB elements and the lanthanides; (iii) when the substance, X, is a compound of the formula M where G is an alkali metal, Z an anion and x the valency of Z, then (a) X is selected such that it will not precipitate Wal from the RA1Hal 4 melt, and (b) X is not a Y1 halide, such as EF; a pseuC'Lohalide, such as k' W; M 2 0 or M 2 CO 3 According to a second aspect of the invention, there is provided a method of making an electrochemical cell of the type comprising an anode compartment containing, at the operating temperature of the cell and when the cell is in its discharged state, a molten alkali metal anode, and a cathode compartment containing, at said operating temperature and in 0 said discharged state, an alkali metal aluminium halide molten salt electrolyte which is also molten at the operating C.

temperature of the cell, and having the fomula MAlHal 4' wherean A is tne alkali metal of the anode and Hal is a halide, the canoae compartment containing also a cathode which comprises an electronically conductive electrolyte -permeable matrix which has dispersed therein an active cathode substance which includes a transition metal T selected from the group comprising Fe, Ni, Co, Cr, Cu, Nin and mixtures thereof, the matfix being impregnated with said electrolyte, and, separating the anode compar - tment from the cathode compartment, a separator which comprises a solid conductor of the ions of the alkali metal of the anode or a 4 k micromolecular sieve which contains said alkali metal sorbed therein, which method comprises loading into a cathode compartment of a cell housing comprising an anode compartment separated from a cathode compartment by a separator which is a solid conductor of ions of alkali metal M or is a micromolicular sieve which contains alkali metal M sorbed therein, an alkali metal aluminium halide molten salt electrolyte having the formula MAlHa14 wherein M is the alkali metal of the separator and Hal is a halide; an alkali metal halide M Hal wherein M and Hal are respectively the same alkali metal and halide as in the molten salt electrolyte; an active cathode substance which comprises a transition metal T selected from the group comprising Fe, Ni, Co, Cr, Cu, Mh and mixtures thereof; and as an additive, at least one further substance, X, thereby to form an electrochemical cell precursor, with X being capable, when the cell precursor is subjected to charging at a temperature at which the molten salt electrolyte and alkali metal M are molten, of reacting at a voltage lower than the voltage required to charge the cell according to the cathode compartment reaction 31Hal+T -:Y 2M+THal 2 (1) and with the provisos that (i) the additive X is compatible with the molten salt electrolyte, the separator and the active cathode substance; (ii) when the substance, X, is an element, it is (a) not AI or Zn, or a mixture of Al and Zn, and (b) not selected from the d- block transition elements of the periodic table of elements, apart from Group MB elements and the lanthanides; (iii) when the substance, X, is a compound of the formula G X Z where G is an alkali metal, Z an anion and x the --5- valency of Z, then (a) X is selected such that it will not precipitate Wal from the MA1Hal 4 melt, and (b) X is not a M halide, such as MF; a pseudohalide, such as WN; M 2 0 or M 2 CO 3; and charging the precursor at a temperature at which the molten salt electrolyte and alkali metal M are molten, to generate alkali metal in the anode compartment such that, after substantially all the substance X has reacted, a cell in discharged state results, the cell in discharged state being chargeable to cause the active cathode substance to be halogenated, with alkali metal M or further alkali metal M being produced and passing through the separator into the anode compartment, the proportions of alkali metal halide Wal, molten salt electrolyte and additive loaded into the cathode compartment being selected so that when the cell is fully charged and all the available active cathode substance has been halogenated, the proportion of alkali metal ions and aluminium ions in the electrolyte is such that the solubility of the active cathode substance in the molten electrolyte is at or near its minimum.

The molar proportion or ratio of alkali metal ions and aluminium ions in the electrolyte is preferably not less than one., to obtain said minimum solubility.

The alkali metal, M, may be sodium, and the separator may be beta-alumina.

The halide may be chloride, so that the alkali metal halide is sodium chloride. The electrolyte may then be in the form of a sodium chloride aluminium chloride mixture or in the form of the double salt, ie NaAlC1 4' The transition metal T of the active cathode substance may be a member of the group comprising Fe, Ni and mixtures thereof.

The additive X will normally also be selected, by bearing one or more of the following in mind:

- it should be temperature -stable over a relatively wide range of temperatures; it should have a relatively low toxicity; its cost should not be excessive; it should not react unfavourably with the beta alumina or any other ion conductor used, causing a resistance rise or physical breakdown of the beta alumina under cell operating conditions such as overcharge, overdischarge, excessively high temperatures.

By 'compatible', in respect of the additive X is meant that it must not partake in any unacceptable side reactions during charging, discharging, overcharging and overdischarging of the cell or precursor, ie reactions which lead to corrosion, increased resistance, loss of capacity, and the like. In other words, the additive must be stable in the environment of the cell or precursor, during all states of charge thereof.

In a first embodiment of the invention, the substance X may be an element having a most common oxidation state of +3. During charging up to the discharged state, the following reactions then take place in the cathode compartment:

3NaCI + X 3Na + XCI, 3 (2) xCl. 3 + NaCi NaRl. 4 (3) wherein NaM 4 is at least partially miscible with the liquid electrolyte. In this case, X may be selected from the elements of Groups IIIA and HIB of the periodic Table of Elements (except aluminium), the lanthanides and bismuth.

- r In a second embodiment of the invention, the substance X may be an element having a most common oxidation state of +2. During charging up to the discharged state, the following reactions then take place in the cathode compartment:

2NaC1 + X:PMa + XCl 2 (4) XCL7 + 2NaC1 Na XCl 2 4 (5) wherein NaXCl 4 is electrochemically and chemically compatible with the liquid electrolyte, with the position of the equilibrium in reaction (5) being dependent on the temperature and nature of the chloride. In this case, X may be selected from the elements of Group IIA and Group IIB (except zinc).

In the first and second embodiments, the method thus initially involves the consumption of the additive and alkali halide starting materials with the formation of a chloride in the cathode compartment and the migration of excess alkali metal into the anode compartment. By 'excess alkali metal' is meant more alkali metal than is required to satisfy the normal electrochemical discharging reaction in the cell, viz:

31 + THal 2;P. 2NIHal + T (6) where T is the transition metal.

In a third embodiment of the invention, X can be a compound of the formula G x Z where G and Z are as hereinbefore defined, provided that G X Z is not the same as MHal. Preferably, G is sodium, with Z being selected such that it and Na x Z is electrochemically and chemically compatible with the liquid electrolyte, the solid electrolyte and the cathode. The compounds Na x Z thus have the following reaction on charging:

Na Z Z + xNa (7).

The compound Na X Z can be Na 3 pp Na 2 S or other sulphur-containing compounds of the formula Na X S y, where y is an integer, NaxSe y, or Na 2S04 A In the third embodiment of the invention the method thus involves the consumption of the further alkali metal compound starting material, the release of Z into the cathode compartment, and the migration of excess alkali metal into the anode compartment. Z goes into the electrolyte or reacts with the active cathode substance.

Sufficient additive is provided so that upon charging up to the discharged state the dissociation of the additive according to reaction (7) provides the initial upstarting amount sodium in the anode compartment, with normal charge and discharge reactions of the cell between its fully charged and fully discharged states, in accordance with reaction (6), thereafter taking place.

An electrochemical cell made in accordance with the method of the present invention can thus initially contain no alkali metal in its anode compartment. In other words, it can be made in fully discharged form.

Furthermore, in use, ie after an electrochemical cell has been subjected to at least one charge cycle, it is often highly desirable that the cell be able to take a significant degree of overdischarge. In the case of an electrochemical cell made in accordance with the method of the present invention, on overdischarge, some of the excess alkali metal in the anode compartment passes through the separator into the cathode compartment. The excess alkali metal hence ensures that, when overdischarging the cell, its anode compartment does not reach the potentially hazardous state of being 'dry', ie containing no alkali metal, or being anode limited. This can result in the separator being damaged during the overdischarge and/or during a subsequent charging cycle due to a high current density being applied to parts of the separator.

f 1 Overdischarging can be obtained, for example, when a number of such cells are connected together in a battery. There is usually a degree of capacity mismatch between the cells which may be aggravated as the cells are subjected to charging/discharging cycles. When the battery is cycled according to the average cell performance, at least some cells will reach an overdischarged state.

Hence, when the transition metal is metallic Fe, it may be in the form of iron powder or filings, and the additive may then be present as a surface coating or alloy on the iron powder or filings. In particular, when the transition metal is in the form of iron filings, the additive may be present in the form of a surface coating, alloy, eg analogously to the socalled Raney Process, sheet, rod or any other suitable form in which it is contacted with the current collector.

In yet another version of the invention, the active cathode substance may be loaded into the cathode compartment in the form of an intermediate refractory hard metal compound of said transition metal T with at least one non-metal of the group consisting of C, Si, B, N, and P.

The active cathode substance and the alkali metal halide may be mixed together in particulate form, eg granules, to form a mixture, the mixture sintered to form an electrolyte-permeable matrix, and the matrix impregnated with the molten salt electrolyte prior to loading thereof into the cathode compartment. If the additive is then in particulate form it can form part of this mixture which is sintered.

When the transition metal is in the form of-an intermediate refractory hard metal compound, the compound can be a carbide eg iron, chromium or manganese carbide. In other embodiments, the compound may comprise a compound of at least one of the i lk- transition metals with a plurality of the non-metals, and/or a compound of a plurality of the transition metals with at least one of the non- metals. The compound may comprise another or second transition metal which is mixed or alloyed with the other or first transition metal. The second transition metal may constitute a minor proportion, eg less than 30%, of the alloy or mixture.

When the transition metal is iron, the cathode may include a small proportion of nickel and/or a chalcogen; and when the transition metal is nickel the cathode may include a small proportion of iron and/or a chalcogen such as sulphur.

When the matrix comprises at least one intermediate refractory hard metal compound it is, once said electrolyte has been impregnated therein and the NaCl and additive are incorporated therein., a cathode precursor which is coupled via the separator with the anode compartment and which becomes a cathode after it has been subjected to at least one charge cycle.

More specifically, forming the matrix may comprise sintering particles such as powders or fibres of the transition metal or intermediate refractory hard metal compound in a reducing atmosphere. Instead, forming the matrix may comprise forming a particulate mixture thereof with an organic binder, pressing the mixture into a unitary body and cracking the binder by heating the mixture under vacuum at a temperature above 4000C, which is sufficient to pyrolyse the binder. For example a carbide of the transition metal in question can be mixed with a small quantity of a carbon-forming organic binder such as phenol formaldehyde resin, the resulting mix being pressed into an electrode shape, and the resin cracked in a vacuum at a temperature above 600'C, which temperature is selected to pyrolyse the binder to conductive carbon.

Incorporating the NaCl and the additive into the matrix may be effected simultaneously with the formation of the matrix, the NaCl and additive in finely divided particulate form being dispersed into the particulate material, eg granules, from which the matrix is formed, prior to formation of the matrix. Such granules can have an extremely high density. Hence, the incorporation into the granules of the additive results in additional porosity when the cell precursor is subjected to a first charging cycle in which it is transformed into a cell in discharged state, as hereinbefore described. Granulation also promotes homogeneity of chemical species within the cathode compartment.

Instead, the NaC1 and additive may be incorporated into the matrix by melting the electrolyte and suspending particulate NaCl and additive in finely divided form in the molten electrolyte, prior to impregnating the electrolyte into the matrix, and then impregnating the electrolyte together with the NaCl and additive suspended therein, into the matrix.

It is hence apparent from the foregoing that the NaCl and additive may be incorporated into the matrix in any one of a number of suitable different ways.

Impregnating the molten salt electrolyte into the matrix may be by means of vacuum impregnation with the electrolyte in the molten state.

When the refractory hard metal compound is present, conditioning of the cell by subjecting it to charge/discharge cycles may be necessary to activate it by halogenation of the intermediate refractory hard metal compound to bring it up to its maximum potential operating performance in the cell.

i In another more specific version of the invention, the NaCl, additive and the transition metal may be combined by forming a mixture in particulate form of NaCl, additive and the transition metal. Still more particularly, the formation of th6 mixture may comprise mixing together a NaCl powder, the additive in powder form and a powder of the transition metal or compound thereof. Suitable iron and nickel powders are available from William Rowland Limited as 'TYPE C CARBONYLI and 'TYPE 225 CARBONYLI respectively.

Instead. the NaCl, additive and transition metal particles can be mixed after loading thereof into the cathode compartment.

The powder mixture may then be impregnated, eg saturated with the electrolyte, which may be effected simply by wetting the mixture with the electrolyte in molten liquid form, for example after the powder mixture has been packed, for exanple by tamping, into the cathode compartment. This will, in effect, provide a cathode precursor in a discharged state, which can then be activated by charging.

compartments In other words, there can initially be loaded into the cathode either an electronically conductive electrolyte-permeable matrix or a matrix precursor capable of becoming such a matrix on the cell being subjected to at least one charge cycle.

In the charging reaction of this precursor, the metal or intermediate refractory hard metal compound component of the mixture is chlorinated, sodium being produced during the chlorination, which sodium moves through the separator in ionic form, into the anode compartment where 'it exists in the charged or partially charged cell as molten sodium metal, electrons passing during the charging along the external circuit from the cathode compartment to the anode compartment.

When making a cell in accordance with the present invention, it is accordingly in principle unnecessary to provide any sodium in the anode compartment, the sodium being produced during activation in the first charging cycle, although it may be desirable to charge a starting amount of sodium into the anode compartment to provide for current collection and to facilitate charging by wetting the separator. However, it is essential that the anode compartment current collector be in intimate electrical contact with substantially the entire separator, to ensure proper function of the cell on initial charging.

Although the powder mixture may be charged in powder form after saturation with liquid electrolyte, the method may include as mentioned hereinbefore the additional step of sintering the powder mix to form a macroporous electrolyte permeable matrix prior to saturation with electrolyte, and activation by taking it through one or more charge cycles as a cathode to chlorinate it.

The invention also extends to an electrochemical cell, when made according to a method as hereinbefore described.

According to a third aspect of the invention, there is provided a precursor for a high temperature electrochemical cell which comprises a cell housing having an anode compartment and a cathode compartment separated from each other by a separator which comprises a solid conductor of ions of an alkali metal M or a micromolecular sieve which contains alkali metal M sorbed therein, the cathode compartment containing:

an alkali metal aluminium halide molten salt electrolyte having the formula MAlHal 4 wherein M is the alkali metal of the separator and Hal is a halide; a cathode which comprises an active cathode substance which includes a transition metal T selected from the group comprising Fe, Ni, Co, Cr, Cu, Mn and mixtures thereof; an alkali metal halide M Hal wherein M and Hal are respectively the same alkali metal and halide as in the molten salt electrolyte; and as an additive, at least one further substance, X, which is capable, when the cell precursor is subjected to charging at a temperature at which the molten salt electrolyte and alkali metal M are molten, of reacting at a voltage lower than the voltage -required to charge the cell according to the cathode compartment reaction Mal+T 2M+THal 2 (1) to generate alkali metal in the anode compartment such that, after substantially all the substance X has reacted, a cell in discharged state results, the cell in discharged state being chargeable to cause the active cathode substance to be halogenated, with alkali metal M or further alkali metal M being produced and passing through the separator into the anode compartment, the proportions of alkali metal halide NHal, molten salt electrolyte and additive being selected so that when the cell is fully charged and all the available active cathode substance has been halogenated, the proportion of alkali metal ions and aluminium ions in the electrolyte is such that the solubility of the active cathode substance in the molten electrolyte is at or near its minimum, with the provisos that (i) the additive X is compatible with the molten salt electrolyte, the separator and the active cathode substance; when the substance. X, is an element, it is not (a) AI or Zn, or a mixture of Al and Zn, and (b) not selected from the d-block transition elements of the periodic table of elements, apart from Group HIB elements, and the lanthanides...

(ii) 9 6 k_ when the substance, X, is a compound of the formula GZ where G i s an alkali metal, Z an anion and x the valency of Z, then (a) X is selected such that it will not precipitate Wal from the MHal 4 melt, and (b) X is not a M halide, such as MF; a pseudohalide, such as WN; M 2 0 or M 2 CO 3 As mentioned hereinbefore, the active cathode substance as well as the alkali metal halide may be in particulate form, eg granules, with the alkali metal halide being mixed with the active cathode substance, and the mixture being impregnated with the molten salt electrolyte. The additive may be particulate and form part of said mixture, or form part of the granules.

In another embodiment of the invention, the cathode may comprise an electronically conducted electrolyte -permeable matrix in which the active cathode substance and alkali metal halide are dispersed, the matrix being impreginated with the molten salt electrolyte.

In yet another embodiment of the invention, the cathode of the cell may comprise an electronically conductive electrolyte permeable macroscopically porous matrix having a chlorinated 0 nickel -containing active cathode substance dispersed therein and the electrolyte and/or active cathode substance containing a minor proportion of a suitable chalcogen dispersed therein for resisting a progressive drop in the capacity of the cathode with repeated charge/discharge cycling thereof.

0 The substance may include NiCl 2 itself, one or more compounds of nickel which have been chlorinated, or combinations of the aforegoing. In a particular embodiment, the matrix itself may 0 comprise nickel, with the substance comprising NiCl 2 Instead, the matrix may comprise a material which does not contain nickel, the substance then comprising an intermediate refractory hard metal compound of nickel, such as a phosphide, boride or silicide thereof, which has been activated by halogenation.

It will be appreciated that minor quantities of impurities may be tolerated in the electrolyte, ie substances which will ionize in the molten electrolyte to provide ions which affect the electrochemical action of the electrolyte, but the quantity of such impurities should be insufficient to alter the essential character of the electrolyte as an MAlHal 4 system as defined.

When the cathode includes iron as a transition metal in conjunction with a beta-alumina solid electrolyte or separator, it may also include a protective cathode substance which oxidizes by chlorination at a voltage less than the open circuit voltage of the Fe/FeCl 3 //Na plateau, and greater than the open circuit voltage of the cathode in its fully charged state when coupled with a sodium anode.

The cathode may comprise Fe/FeCl 2 as an active cathode substance dispersed in the matrix, the protective cathode substance oxidizing by chlorination at a voltage greater than the open circuit voltage of the Fe/FeCl 2 //Na plateau.

The protective cathode substance may be dispersed in finely divided form through the cathode, and the protective cathode substance may be selected from the group consisting in Ni/NiCl 21 CO/COC1 2 and combinations of Ni/NiCl 2 and Co/CoCl 2 When the separator is a micromolecular sieve, it may be a tectosilicate, eg a felspar, felspathoid or zeolite. When it is a zeolite. the zeolite may be a synthetic zeolite such as zeolite 3A. 4Ay 13X, or the like. Preferably, however, the 1 1 I& separator is a solid conductor of sodium ions such as beta-alumina or nasicon. For example, a beta-alumina tube can be used. The interior of the tube may be used as the anode compartment, with the tube being located in a cell housing which defines a cathode compartment outside the tube, in the interior of the housing, and with an anode compartment current collector being in intimate electrical contact with substantially the entire separator. The tube will be sealed and may be evacuated prior to charging to resist undesirable pressure build-up therein as sodium moves into the anode compartment during charging, through the tube wall. In this specification, beta-alumina is used broadly to include all phases of sodium-ion conducting beta-alumina, such as beta"-alumina.

To spread the sodium over the inside of the tube wall and to effect said intimate contact of the anode compartment current collector with the separator, suitable wicking material, electrically connected to the current collector and containing finely divided electrically conductiveparticles, may be spread over the wall surface. The material may, for example, be iron mesh, optionally tinned. This mesh hence acts as a part of an anode current collector, and may be attached to an evacuation pipe of the same metal, used to evacuate the tube interior prior to charging and projecting out of the cell to form the remainder of the anode current collector.

The main current collector of the cathode of the cell of the present invention will usually be the housing itself which may be a metal such as the metals employed in the cathode powder combination or mixture. In this case, the housing may be the same metal as that of the powder mixture, or one with a higher charging potential, so that it remains metallic at all times. To improve the initial activation or charging characteristics of the cell, the cathode current collector may include a metal 4 mesh or gauze connected, for example by welding, to the housing.

For close packing in batteries, the cell may have an elongate rectangular housing along the interior of which the tube extends in a more or less central position. To facilitate wicking in the anode compartment, the cell may be used horizontally, but this can lead to voids in the cathode compartment formed upon. charging as the sodium moves into the anode compartment. For this reason, the cell may incorporate an electrolyte reservoir, more or less separate from but in communication with the cathode compartment, from which the electrolytes can pass, for example by draining under gravity, into the cathode compartment to keep it flooded with liquid electrolytes at all times. Naturally, for close packing, cells of similar construction but having an -hexagonal cross-section can be employed instead.

The electrolyte may include a minor proportion of sodium fluoride as dopant. This combats potential progressive internal resistance rise on cell cycling and the invention accordingly contemplates incorporating a small proportion of sodium fluoride in the powder mix from which the cathode is formed, when it contains Fe as an active cathode substance. This sodium fluoride dissolves in the liquid electrolyte, in use. The electrolyte should be selected so that, at all states of charge, the solubility therein of FeCl 2 is at a minimum. This is achieved when the electrolyte comprises a mixture of sodium halide and aluminium halide in a 1:1 mole ratio, with the molten salt being in the presence of at least some solid sodium chloride at all stages of charge. The only alkali metal present should be those which do not adversely affect the beta-alumina separator, and, although pure sodium aluminium chloride can be used, said minor proportion of up to 10% on a molar basis or more of the electrolyte may be made up of sodium fluoride. The sodium fluoride will replace the equivalent proportion of sodium chloride, so that said 1: 1 mole ratio is retained. The proportion of sodium fluoride will, however, be sufficiently low for the electrolyte to retain its essential character as a sodium aluminium chloride electrolyte. There must thus be enough sodium chloride, as mentioned above, for some solid sodium chloride to remain in the cathode compartment when the cell is fully charged, ie to maintain minimum solubility.

As mentioned hereinbefore, the liquid electrolyte and/or active cathode substance may contain a minor proportion of a suitable chalcogen dispersed therein for resisting a progressive drop in the capacity of the cathode -with repeated charge/discharge cycling of the cell, when the cathode contains, in the matrix, a chlorinated nickel- containing substance dispersed therein as the active cathode substance.

The chalcogen may comprise one or more species, such as selenium or sulphur, or compounds containing sulphur such as a transition metal sulphide. The chalcogen is preferably in extremely finely divided form, and it or reaction products between it and components of the liquid electrolyte may even be dissolved in the electrolyte.

The invention will now be described, by way of example, with reference to the accompanying diagrammatic drawing, in which the single figure shows a schematic sectional side elevation of an electrochemical cell in accordance with the present invention.

In the dra;%ring, reference numeral 10 generally indicates an electrochemical cell in accordance with the invention.

The cell 10 includes an outer cylindrical casing 12 having a side wall 22 connected to a circular floor 24; a beta-alumina tube 14 located concentrically within the casing 12, the tube 14 being closed at its one end 16 and open at its other end 18; and a collar assembly 20 around the end 18 of the tube 14. The collar assembly 20 comprises a circular insulating ring 26 of alpha-alumina, with the end 18 of the tube 14 mounted to the ring 26 by being sealingly located in an annular groove 28 in the ring. Two concentric truncated : nickel, designated 30,32, are bonded fluid cylinders o-IL tightly to the outer and inner curved surfaces respectively of the ring 26. An annular closure disc 34 closes off the open end 18 of the tube 14, the disc 34 being secured to the truncated cylinder or ring 32 at 36. An annular disc 40 also closes off the end of the casing 12 remote from the floor 24, the disc 40 being secured, e.g. welded, to the casing at 42 and to the ring 30 at 44. A steel rod current collector 46 projects into the tube 14, and a steel rod current collector 50 protrudes from the disc 40 at 52. The current collector 46 is electrically connected to a porous wicking layer 47 lining the inside of the separator tube 14, ie in intimate contact with the tube 14, with finely divided electrically conductive particles, eg Ni and/or Fe particles incorporated in the layer.

An anode compartment 56 is hence provided inside the tube 14, with a cathode compartment 58 being provided around the outside of the tube 14, within the casing 12, the beta-alumina tube 14 hence constituting a separator between the anode and cathode compartments.

Into the cathode compartment 58 there is placed an electrolyte permeable matrix 60 of Fe, with sodium chloride and sodium phosphide powder, as an additive, incorporated therein in dispersed form. The anode compartment 56 initially contains 1 no anode material. Sufficient molten NaAlCl 4 electrolyte is then added to the cathode compartment so that the matrix is impregnated with the electrolyte and the electrolyte wets the separator or tube 14. The beta- alumina tube 14 hence forms a continuous barrier between the electrolyte containing cathode compartment 58 and the anode compartment 56, within the housing 12. Initially, the layer 47 ensures the required electrical contact between the collector 46 and the separator 16. However., on the first sodium passing through the separator it 'wicks' along the layer 47 thereby providing further electrical contact between the anode compartment and the separator.

On charging the cell 10, the following reactions take place in the cathode compartment Na 3 p 3Na + P (8) NaCl + Fe Na + FeCl 2 (9) The Na generated by reactions (8) and (9) passes through the beta-alumina into the anode compartment. Hence, the Na generated by dissociation reaction (8) is excess Na, which will permit overdischarging of the cell as hereinbefore described. A small amount of starting Na can be provided in the anode compartment, in molten form, to connect the current collector 46 to the separator 14, but it is envisaged that this will not normally be the case since an anode which is initially sodium-free provides important advantages eg the cell can be transported readily and safely.

However, once the cell has been subjected to repeated charge/discharge cycles, the "excess" sodium chloride initially present in the cathode compartment will ensure that there is at all times sufficient sodium in the anode compartment to keep the entire surface of the separator 14 covered with sodium, even when the cell is over discharged as 1 hereinbefore described. Failure to keep the entire separator covered with sodium will lead to high current densities being imposed on the separator, resulting in inefficient operation, ie anode limited and possible premature failure.

Instead, there can be placed into the cathode compartment 58 an electrolyte permeable matrix 60 of Fe, with sodium chloride and magnesium powder, as an additive, incorporated therein in dispersed form. The anode compartment 56 again initially contains no anode material.. Sufficient molten NaCC14 electrolyte is then added to the cathode compartment so that the matrix is impregnated with the electrolyte and the electrolyte wets the separator or tube 14.

The cathode compartment 58 contains sufficient NaCl and Mg so that, on charging the cell 10, the following reactions take 0 place in the cathode compartment:

2NaCl + Mg 2Na + MgC1 2 (10) 2NaCl + MgC1 2 Na 2'9C'4 (11) 2NaCl + Fe 2Na + FeCl 2 (12).

The Na generated by reactions (10) and (12) passes through the betaalumina into the anode compartment. gence, the Na generated by reaction (10) is excess Na, which will permit overdischarging of the cell as hereinbefore described. However, again, once the cell has been subjected to repeated charge/discharge cycles, the 'excess' sodium chloride initially present in the cathode compartment will ensure that there is at all times sufficient sodium in the anode compartment to keep the entire surface of the separator 14 covered with sodium, even when the cell is overdischarged, as hereinbefore described. Failure to keep the entire separator covered with sodium will lead to high current densities being imposed on the separator, resulting in inefficient operation, ie anode limited and possible premature failure.

k Furthermore, the magnesium which is initially introduced into the cathode compartment should be located in such a manner that the MgC12 which is formed will not readily poison the separator 14. For example, the magnesium may be in the form of thin sheets (not shown) located physically remote from the separator 14 and electrically connected to the cathode current collector 50.

1 1

Claims

Claims:

1. A method of making a precursor for an electrochemical cell of the type comprising an anode compartment containing, at the operating temperature of the cell and when the cell is in its discharged state, a molten alkali metal anode., and a cathode compartment containing, at said operating temperature and in said discharged state, an alkali metal aluminium halide molten salt electrolyte which is also molten at the operating temperature of the cell, and having the formula MAIHal 41 wherein M is the alkali metal of the anode and Hal is a halide, the cathode compartment containing also a cathode which comprises an electronically conductive electrolyte -permeable matrix which has dispersed therein an active cathode substance which includes a transition metal T selected from the group comprisin g Fe, Ni, Co, Cr, Cu, Mn and mixtures thereof, the matrix being impregnated with said electrolyte, and, separa-Eing the anode compartment from the cathode compartment, a separator which comprises a solid conductor of the ions of the alkali metal of the anode or a micromolecular sieve which contains said alkali metal sorbed therein, which method comprises loading into a cathode compartment of a cell housing comprising an anode compartment separated from a cathode compartment by a separator which is a solid conductor of ions of alkali metal M or is a micromolecular sieve which contains alkali metal M sorbed therein, an alkali metal aluminium halide molten salt electrolyte having the formula MAlHal 4 wherein M is the alkali metal of the separator and Hal is a halide; an alkali metal halide M Hal wherein M and Hal are respectively the same alkali metal and halide as in the molten salt electrolyte; i an active cathode substance which comprises a transition metal T selected from the group comprising Fe, Ni, Co, Cr, Cu, Nin and mixtures thereof; and as an additive, at least one further substance, X, thereby to form an electrochemical cell precursor, with X being capable, when the cell precursor is subjected to charging at a temperature at which the molten salt electrolyte and alkali metal M are molten, of reacting at a voltage lower than the voltage required to charge the cell according to the cathode compartment reaction 31Hal+T 31+THal

2 (1) to generate alkali metal in the anode compartment such that, after substantially all the substance X has reacted, a cell in discharged state results, the cell in discharged state being chargeable to cause the active cathode substance to be halogenated, with alkali metal M or further alkali metal M being produced and passing through the separator into the anode compartment, the proportions of alkali metal halide NHal, molten salt electrolyte and additive loaded into the cathode compartment being selected so that when the cell is fully charged and all the available active cathode substance has been halogenated, the proportion of alkali metal ions and aluminium ions in the electrolyte is such that the solubility of the active cathode substance in the molten electrolyte is at or near its minimum, with the provisos that (i) the additive X is compatible with the molten salt electrolyte, the separator and the active cathode substance; when the substance, X, is an element, it is (a) not Al or Zn, or a mixture of Al and Zn, and (b) not selected from the d-block transition elements of the periodic table of elements, apart from Group INB elements and the lanthanides; when the substance, X, is a compound of the formula G X Z where G is an alkali metal, Z an anion and x the (ii) (iii) valency of Z, then (a) X is selected such that it will not precipitate Mial from the MA1Hal 4 melt, and (b) X is not a M halide, such as ME; a pseudohalide, such as MCK; M 2 0 or M 2C0 3 2. A method according to Claim 1J. wherein the alkali metal, M, is sodium; the separator is beta-alumina; the halide is chloride, so that the alkali metal halide is sodium chloride; the electrolyte is in the form of a sodium chloride aluminium chloride mixture or in the form of the double salt NaAlCl 4; and the transition metal T of the active cathode substance is a member of the group comprising Fe, Ni and mixtures thereof.

3. A method according to Claim 2, wherein the substance X is an element having a most common oxidation state of +3 so that during charging up to the discharged state, the following reactions then take place in the cathode conTartment:

3NaCl + X 3Na + XCl 2) 3 C' Xcl 3 + NaCl - b= NaM 4 (3) wherein Na.= 4 is at least partially miscible with the liquid electrolyte and is chemically and electrochemically compatible therewith.

4.. A method according to Claim 3, wherein X is selected from the elements of Groups IIIA and HIB of the periodic Table of Elements (expept aluminium), the lanthanides and bismuth.

5. A method according to Claim 2, wherein the substance X is an element having a most common oxidation _state of +2 so that during charging up to the discharged state, the following reactions then take place in the cathode compartment:

2NaCl + X - 2Na + XCl 2 Xcl 2 + 2NaCl Na 2 Xcl 4 ......... (4) (5) 1 wherein NaXCl 4 is electrochemically and chemically compatible with the liquid electrolyte and is partially therewith.

6. A method according to Claim 5, wherein X is selected from the elements of Group IIA and Group IB (except zinc).

7. A method according to Claim 2, wherein X is a compound of the formula GxZ where G and Z are as hereinbefore defined, with G being sodium, and with Z being selected such that it and Na X Z is electrochemically and chemically compatible with the liquid electrolyte, the solid electrolyte and the cathode with the compound Na X Z thus having the 0 following reaction on charging Na Z X ................ (7).

8. A method according to Claim 7, wherein the compound NaXZ is Na,P, Na,S or other sulphur -containing compounds of the formula Na X S y, where y is an integer, Na X Se Y, or Na 2 SO 4.

9. A method according to any one of Claims 2 to 8 inclusive, in which the additive is load ed into the cathode compartment in particulate form.

10. A method according to any one of Claims 2 to 9 inclusive, in which the active cathode substance is loaded into the cathode compartment as the transition metal T in metallic form.

11. A method according to any one of Claims 2 to 9 inclusive, in which the active cathode substance is loaded into the cathode compartment in the form of an intermediate refractory hard metal compound of said transition metal T with at least one non-metal of the group comprising C, N, B, Si, 0 and P.

1 k

12. A method according to any one of Claims 1 to 11 inclusive, in which the active cathode substance and the alkali metal halide M Hal are loaded into the cathode in particulate form, the particles in the cathode compartment are mixed, and the mixture is impregnated with the molten salt electrolyte.

13. A method according to any one of Claims 1 to 11 inclusive, in which the active cathode substance and alkali metal halide are mixed together in particulate form to form a mixture., the mixture is sintered to f orm an electrolyte -permeable matrix, and the matrix is impregnated with the molten salt electrolyte prior to loading thereof into the cathode compartment.

14. A method according to any one of the preceding claims, in which alkali metal M is loaded into the cathode compartment in metallic form and reacts with the molten salt electrolyte to produce alkali metal halide MHal and aluminium in metallic form.

is. A method according to Claim 14 in which the alkali metal is loaded into the cathode compartment impregnated into a porous carrier.

16. A method of making a precursor for an electrochemical cell, as claimed in claim 1, substantially as described herein.

17. An electrochemical cell precursor when made in accordance with the method as claimed in any one of claims 1 to 16 inclusive.

18. A method of making an electrochemical cell of the type comprising an anode compartment containing, at the C, 91 operating temperature of the cell and when the cell is in its discharged state, a molten alkali metal anode, and a cathode compartment containing, at said operating temperature and in said discharged state, an alkali metal aluminium halide molten salt electrolyte which is also molten at the operating temperature of the cell, and having the formula NJAlHa'41 wherein M is the alkali metal of the anode and Hal is a halide, the cathode compartment containing also a cathode which comprises an electronically conductive electrolyte -permeable matrix which has dispersed therein an active cathode substance which includes a transition metal T selected from the group comprising Fe, Ni, Co, Cr, Cu, Mn and mixtures thereof., the matrix being impregnated with said electrolyte, and, separating the anode compartment from the cathode compartment, a separator which comprises a solid conductor of the ions of the alkali metal of the anode or a micromolecular sieve which contains said alkali metal sorbed therein, which method comprises loading into a cathode compartment of a cell housing comprising an anode compartment separated from a cathode compartment by a separator which is a solid conductor of ions of alkali metal M or is a micromolecular sieve which contains alkali metal M sorbed therein, an alkali metal aluminium. halide molten salt electrolyte having the formula MAlHal 4 wherein M is the alkali metal of the separator and Ha 1 is a halide; an alkali metal halide M Hal wherein M and Hal are respectively the same alkali metal and halide as in the molten salt electrolyte; an active cathode substance which comprises a transition metal T selected from the group comprising Fe, Ni, Co, Cr, Cu, Mn and mixtures thereof; and as an additive, at least one further substance, X, thereby to form an electrochemical cell precursor, with X being capable, when the cell precursor is subjected to J charging at a temperature at which the molten salt electrolyte and alkali metal M are molten, of reacting at a voltage lower than the voltage required to charge the cell according to the cathode compartment reaction 2MHal+T 2M+THal 2 (1) and with the provisos that the additive X is compatible with the molten salt electrolyte, the separator and the active cathode substance; (i) (iii) when the substance, X, is an element, it is (a) not Al or Zn, or a mixture of Al and Zn, and (b) not selected from the d-block transition elements of the periodic table of elements, apart from Group MB elements and the lanthanides; when the substance, X, is a compound of the formula G X Z where G is an alkali metal, Z an anion and x the valency of Z, then (a) X is selected such that it will not precipitate M-lal from the LUHal 4 melt. and (b) X is not a M halide, such as MF; a pseudohalide, such as IvIGN; M 2 0 or MI 2 CO 3; and charging the precursor at a temperature at which the molten salt electrolyte and alkali metal M are molten, to generate alkali metal in the anode compartment such that, after substantially all the substance X has reacted, a cell in discharged state results, the cell in discharged state being chargeable to cause the active cathode substance to be halogenated, with alkali metal M or further alkali metal M being produced and passing through the separator into the anode compartment, the proportions of alkali metal halide Wal, molten salt electrolyte and additive loaded into the cathode compartment being selected so that when the cell is fully charged and all the available active cathode substance has been halogenated, the proportion of alkali metal ions and aluminium ions in the electrolyte is such that the solubility i k of the active cathode substance in the molten electrolyte is at or near its minimum.

19. A method according to Claim 18, wherein the alkali metal, M, is sodium; the separator is beta-alumina; the halide is chloride, so that the alkali metal halide is sodium chloride; the electrolyte is in the form of a sodium chloride - aluminium chloride mixture or in the form of the double salt NaAlCl 4; and the transition metal T of the active cathode substance is a member of the group comprising Fe, Ni and mixtures thereof.

20. A method according to Claim 19, wherein the substance X is an element having a most common oxidation state of +3. During charging up to the discharged state, the following reactions then take place in the cathode compartment:

3NaCl + X 3Na + XCl 3 XCl_ + NaCl C---" NaXCl (3) 1) 4 wherein NaXCl 4 is at least partially miscible with the liquid electrolyte and is chemically and electrochemically compatible therewith.

21. A method according to Claim 20, wherein X is selected from the elements of Groups IIIA and HIB of the periodic Table of Elements (except aluminium), the lanthanides and bismuth.

22. -A method according to Claim 19, wherein the substance X is an element having a most common oxidation state of +2 so that during charging up to the discharged state, the following reactions then take place in the cathode compartment:

2NaCl + X 2Na + XCl 2 (4) Xcl 2 + 2NaCl ',c- Na 2 xCl 4 (5) 1 wherein NaXC1 4 is electrochemically and chemically compatible with the liquid electrolyte and is partially miscible therewith.

23. A method according to Claim 22, wherein X is selected from the elements of Group IIA and Group 1IB (except zinc).

24. A method according to Claim 19, wherein X is a compound of the formula GxZ where G and Z are as hereinbefore defined with G being sodium, and with Z being selected such that it and NaxZ is electrochemically and chemically compatible with the liquid electrolyte, the solid electrolyte and the cathode with the compound Na x Z thus having the following reaction on charging:

Naj Z + xNa.................

25. A method according to Claim 24, wherein the compound 0 Na Z is Na3P, Na or other sulphur -containing compounds of X 2S 0 the formula Na S, where y is an integer, Na X Se y, or Na 2 so 4 X y

26. A method according to any one of Claims 19 to 25 inclusive, in which the additive is loaded into the cathode compartment in particulate form.

27. A method according to any one of Claims 19 to 26 inclusive, in which the active cathode substance is loaded into the cathode compartment as the transition metal T in metallic form.

28. A method according to any one of Claims 19 to 26 inclusive, in which the active cathode substance is loaded into the cathode compartment in the form of an intermediate refractory hard metal compound of said transition metal T with at least one non-metal of the group comprising C, N, B, Si, and P.

29. A method according to any one of Claims 19 to 28 inclusive, in which the active cathode substance and the alkali metal halide M Hal are loaded into the cathode in particulate form., the particles in the cathode compartment are mixed, and the mixture is impregnated with the molten salt electrolyte.

30. A method according to any one of Claims 19 to 28 inclusive, in which the active cathode substance and alkali metal halide are mixed together in particulate form to form a mixture, the mixture is sintered to f orm an electrolyte -permeable matrix, and the matrix is impregnated with the molten salt electrolyte prior to loading thereof into 0 the cathode compartment.

31. A method according to any one of Claims 19 to 28 inclusive, in which alkali metal M is loaded into the cathode compartment in metallic form and reacts with the molten salt electrolyte to produce alkali metal halide Wal and aluminium in metallic form.

32. A method according to Claim 31, in which the alkali metal is loaded into the cathode compartment impregnated into a porous carrier.

33. A method of making an electrochemical cell, as claimed in Claim 18, substantially as described herein.

34. An electrochemical cell when made in accordance with the method as claimed in any one of Claims 18 to 33 inclusive.

35. A precursor for a high temperature electrochemical cell which comprises a cell housing having an anode compartment and a cathode compartment separated from each other by a separator which comprises a solid conductor of ions of an alkali metal M or a micromolecular sieve which contains alkali metal M sorbed therein, the cathode compartment containing:

an alkali metal aluminium halide molten salt electrolyte having the formula MAlHal 4 wherein M is the alkali metal of the separator and Hal is a halide; a cathode which comprises an active cathode substance which includes a transition metal T selected from the group comprising Fe, Ni, Co, Cr, Cu, Mn and mixtures thereof; an alkali metal halide M Hal wherein M and Hal are resp ectively the same alkali metal and halide as in the molten salt electrolyte; and as an additive, at least one further substance, X, which is capable, when the cell precursor is subjected to charging at a temperature at which the molten salt electrolyte and alkali metal M are molten, of reacting at a voltage lower than the voltage required to charge the cell according to the cathode compartment reaction Wal+T 2AI+THal 2 (1) to generate alkali metal in the anode compartment such that, after substantially all the substance X has reacted, a cell in discharged state results, the cell in discharged state being chargeable to cause the active cathode substance to be halogenated, with alkali metal M or further alkali metal M being produced and passing through the separator into the anode compartment, the proportions of alkali metal halide NHal, molten salt electrolyte and additive being selected so that when the cell is fully charged and all the available active cathode substance has been halogenated, the proportion of alkali metal ions and aluminium ions in the electrolyte is such that the solubility of the active cathode substance in the molten electrolyte is at or near its minimum, with the provisos that (i) the additive X is compatible with the molten salt electrolyte, the separator and the active cathode substance; 1 when the substance, X, is an element, it is not (a) Al or Zn,' or a mixture of Al and Zn., and (b) not selected from the d-block transition elements of the periodic table of elements, apart from Group HIB elements, and the lanthanides; when the substance, X. is a compound of the formula G.Z where G is an alkali metal, Z an anion and x the valency of Z, then (a) X is selected such that it will not precipitate NEal from the MA1Hal 4 melt. and (b) X is not a M halide, such as W; a pseudohalide, such as MCIN; M 2 0 OT M 2 CO 3

36. A precursor according to Claim 35, in which the active - cathode substance is particulate, and in which the alkali metal halide is particulate and is mixed with the active cathode substance, the mixture being impregnated with the molten salt electrolyte.

37. A precursor according to Claim 36, in which the additive is particulate and forms part of said mixture.

38. A precursor according to Claim 35, in which the cathode comprises an electronically conductive electrolyte-permeable matrix in which the active cathode substance and alkali metal halide are dispersed, the matrix being impregnated with the molten salt electrolyte.

39. A precursor according to Claim 35, substantially as described and illustrated herein.

icon.+rh. Patent Office. State HOUse, 86M Holoorn. london WC1R 4TP. Purther COPICS maybe obtained from The Patent 0Mce.