CA1137551A - Battery cathodes of molybdenum dioxide and molybdenum disulphide - Google Patents

Abstract

BATTERY CATHODE AND METHODS

OF MAKING SAME

ABSTRACT

A battery cathode comprising MoO2 or MoS2 particles coated with MoO2, methods of making same, and cells having a lithium anode together with such cathodes are disclosed.

Description

113755~

BATTERY CATHODE AND METHODS OF MAKING SAME

Field to Which the Invention Relates This invention relates to battery ~athodes and methods of making same for use in secondary battery cells. More particularly, this invention relates to battery cathodes and methods of making same, the cathode-active material comprising molybdenum dioxide ~MoO2) or molybdenum dioxide coating molybdenum disulphide (MoS2).
Mo02 i5 one of a class of compounds having a so-called "rutile-related" structure, the crystallo-graphy of Which has been well characterized in the literature. Further, MoO2 is known to be a metal With room temperature electrical conductivity approximately ten times higher than that of carbon. Some investiga-tion of the electrochemical properties of MoO2 has been done, mainly directed to the use of the material as an oxygen-reduction catalyst.
MoS2 is one of a class of compounds referred to as layered transition metal dichalcogenides, and use of MoS2, as well as other layered transition metal dichalcogenides, as cathode-active materials have been reported in the literature. From the point of view of cost, MoS2 is a desirable substance to use as a cathode-active material - it occurs in nature in sig-nificant quantities and is one of the less expensive layered transition metal dichalcogenides.
A number of techniques for producing coatings on metallic substrates are known. For example, ~,. ' '.

375Sl it is well known to produce a coating on a metallic substrate by painting a mixture of the coating material dissolved or suspended in a carxier onto the substrate to be coated, and then heating to decompose the carrier, lea~ing the coating material adherent to the substrate.
U.S. Patent No. 2,819,962 teaches a method of producing sintered plates for galvanic cells by preparing a suspension of metallic powder having inter-calating properties in water in which a viscosity-increasing agent has been dissolved. The substrate to be coated is dipped in the suspension, the thickness of the coating so obtained is adjusted and then the substrate is heated to dry the coating. The coated substrate is then sintered in a nonoxidizing atmosphere and cut into individual cell plates.
According to U.S. Patent No. 2,905,574, a surface coating of MoS2 may be obtained by coating the surface with a saturated ammoniacal solution of monomethylammonium tetrathiomolybdate and then heating to 480C in a stream of nitrogen.
U. S. Patent No. 3,047,419 teaches a method of producing a corrosion-resistant silicide coating on titanium by painting the titanium to be coated with a carrier liquid in which an organic binder has been dissolved, and in which fine particles of silicon and titanium are suspended. The coated body is dried, then heated in an inert atmosphere to decom-pose and vaporize the carrier and sinter the silicon to leave a silicon-titanium alloy coating.

'~

Some molybdenum compounds have been considered as possible cathode-active materials.
A significant amount of effort has been directed to the study of molybdenum trioxide (MoO3) as a cathode-active material. In connection with these studies, lithium has often been used as the opposing anode-active material. Although MoO3 is of commercial interest be-cause of the possibility that it may be used to fabricate a high energy density battery, it is a relatively poor electrical conductor -- a characteristic which imposes limitations on high current discharge performance. To improve such performance, MoO3 powder is often mixed with a conducting additive such as powdered graphite.
However, the charge-discharge cycle performance of the Li/MoO3 couple appears to be relatively limited.
Although the action of MoO3 with lithium is not well understood, it is generally believed to react or tend to react in a non-reversible manner to form other oxides of molybdenum or compounds such as Li2MoO4.
Recently, MQ8023 has been examined for possible use as a cathode-active mater:ial versus an anode which includes lithium as the anode-active material: see High Energy Density Batteries Based on Lithium Anodes and Substoichiometric Oxide Cathodes in Organic Electrolytes, Power Sources 1977, Vol. VI, pp. 527-536, Pietro et al. However, the Li/Mo8023 couple is believed to involve an irreversible reaction resulting in production of lithium molybdates (Ibid).
An object of the present invention is to .. ..

-~3755~

facilitate the production of a battery cathode using rel-atively inexpensive MoS2 while achieving a high degree of reversibility and discharge rate capability.
SUMMA~Y OF THE INVENTION
In one aspect of the present invention, there is provided a battery cell which comprises a lithium anode, a non-aqueous electrolyte and a cathode having a cathode-active material which comprises MoO2.
The invention also provides a battery cell which comprises a lithium anode, a non-aqueous electrolyte and a cathode having a cathode-active material which comprises Mo02 and MoS2.
The invention further provides a battery cell which comprises a lithium anode, a non-aqueous electrolyte and a cathode having a cathode-active material which con-sists essentially of MoS2 particles coated with MoO2.
Hence, the present invention contemplates the fabrication of battery cathodes, the cathode-active material of which comprises MoO2 or MoO2 coating MoS2.
It has been found that MoO2 itself (viz.
without any substantial amount of MoS2) behaves as a good cathode-active material, and that its presence as a coating on MoS2 particles will improve the discharge rate characteristics over that obtainable where the cathode-active material consists essentially of MoS2 particles. Cells having such cathodes have been found to exhibit a high degree of reversibility.
The electrical conductivity of a cathode is im-proved where a relatively thin coating of M02 appears :13.3~5Sl on MoS2. As the rnole percentage of M02 coating MoS2 is increased in relation to the mole percentage of MoS2, the electrical conductivity of the cathode im-proves with only limited sacrifice of energy density char-acteristics. MoO2 has energy density characteristics `"` 1~37551 somewhat inferior to those of MoS2, but conversely has superior electrical conductivity characteristics.
In given applications, the amount of Mo02 present will be a function of a trade-off hetween energy density requirements and desired high current discharge characteristics. ~f high current discharge performance is not a primary consideration, then only a relatively small amount of Mo02 may be present.
Conversely, if high current discharge performance is of primary importance, then a relatively large amount of Mo02 may be present. Indeed, as indicated above, in some applications the cathode-active material may consist essentially of Mo02 with little or no MoS2 present.
As is described in more detail hereinafter, the present invention lends itself to fabrication using MoS2 as a raw material whether the eventually resulting cathode-active material comprises Mo02 or Mo02 coating MoS2.
DRAWINGS
FIGURE 1 is a cross-sectional front view showing a typical tube furnace having in-stalled a quartz tube containing an aluminum support slab bearing a glass slide on which a foil substrate with applied film to be baked is mounted. Also shown are baking atmosphere in-let and exhaust ports.
FIGURE 2 is a graph showing discharge and recharge characteristics of a cell constructed as' described hereinafter in Example 1. Cell 7~;S~

voltage i5 plotted as the ordinate with time in hours plotted as the abscissa.
FIGURE 3 is a graph showing discharge and recharge characteristics of a cell con-structed as described hereinafter in Example 3.
Cell voltage is plotted as the ordinate with time in hours plotted as the abscissa.
DETAILED DESCRIPTION
The description whi~h follows deals primarily with the fabrication of battery cathodes which have a cathode-active material consisting essentially of MoO~ particles or MoS2 particles coated with MoO2. The fabrication of complete cells which include a lithium anode and a selected electrolyte is discussed in the Examples which appear at the end of the description. The construction of lithium anodes and complete cells ~ -is not discussed in detail because the techniques involved are purely conventional and well known to those skilled in the art.

_ ,~ _ 1~37551 To fabricate from MoS2 a battery cathode which comprises MO2 as a cathode-active materiâl, particles of MoS2 are oxidized to form MoO2 or MoO3.
In cases where MOO2 is formed, it will not necessarily be the case that the MoS2 is completely oxidized to MoO2. In fact, for some applications, it is contem-plated that only a relatively small proportion of the MoS2 present will be oxidized to MoO2. In cases where MoO3 is formed by oxidization of the MoS2, sub-stantially all the MoS2 present is oxidized and there then follows a subsequent reduction step during which substantially all the MoO3 is reduced to MoO2.
Herein, conversion of MoS2 to MO2 or to a mixture of MoS2 and MoO2 will be referred to as "direct conversion" as distinct from "indirect conver-sion", which contemplates conversion from MoS2 to MoO3 followed by conversion of the MoO3 to MoO2.
~a) MoS2 to MOO2 or a mixture of MoS2 and MOO2 .
("direct conversion") A suspension of finely divided MoS2 particles in a suitable suspending media is applied to a metallic substrate.
~arious suspending media are suitable, the primary requisite being that the viscosity be suffi-ciently high to allow handling of the substrate when coated without significant loss of the suspending media from the substrate surface. Preferably, a liquid having a boiling point below the baking temperature (discussed hereinafter) is chosen so that the liquid 1~L3~5~;~

will evaporate before the baking temperature is reached, thus reducing the possibility that the li~uid may interfere with the oxidization process. The in~
ventors suggest the use of a liquid such as propylene glycol as the suspending media.
A variety of metals or metal alloys are suitable for use as a substrate, the primary requisites being that they do not adversely react with MoS2 or MOO2 and do not themsel~es oxidize to produce unaccept-able side effects. Preferred substrate materials in-clude aluminum or titanium or alloys thereof, or stain-less steel. The inventors have found aluminum foil used for ordinary household purposes to be quite accepta- -ble as a substrate. Platinum may be usedj but its cost will likely be considered prohibitive for most commercial applications. Nickel may also be used;
however, problems may be encountered with excessive oxidation of the nickel when the MoS2 particles are oxidized on the substrate. The nickel substrate may lose mechanical rigidity and its electrical conductivity may be degraded. Although the other substrate materials may be oxidized at least in part during the oxidization of MoS2 particles, they do not appear as susceptible to the problems which have been encountered with nickel.
The suspension of finely divided MoS2 par-ticles may be applied to only one or to both faces of the substrate. If the suspension is applied to only one face, then the substrate may be placed with the coated face up on a slab of material such as aluminum which acts as a support during the baking procedure 37SS~

described hereinafter. If the suspension is applied to both faces of the substrate, the substrate should preferably be suspended to permit a free flow of the baking atmosphere past both substrate faces.
The inventors have found it convenient to use as a substrate a strip of aluminum foil having a width approximately equaI to the width of a standard microscope slide. One of the narrower ends of khe strip is bent around one of the narrower ends of the slide. The aluminum foil strip thus mounted on a microscope slide is easy to handle during subsequent - steps of cathode preparation. The inventors advise against bending both ends of the strip around corres-ponding ends of the microscope slide because glass and aluminum have different coefficients of thermal expansion which might result in buckling during baking of the strip.
The suspension is preferably applied to the substrate to yield a film-like coating which is suf-ficiently thin to allow diffusion of oxygen throughoutthe coating in a time which is relatively short com-pared to the reaction time of oxygen with MoS2~ This will encourage the formation of a homogeneously oxi-dized cathode. The time required for oxygen to diffuse throughout the coating has been found to depend upon the average MoS2 particle size in the coating, the packing density of MoS2 particles in the coating, and the baking temperature. It has been found that coat-ings of up to at least 20 mg of MoS2 per cm having an average particle size of about 20 microns may be -, /o _ ,~ _ 11375S~

uniformly oxidized onto an aluminum substrate at temperatures ranging between about 400C to 650C.
The thickness of the coating which may be oxidized onto a given substrate will to some extPnt be governed by the substrate material chosen. The substrate and the coating will likely have different coefficients of thermal expansion, which, depending upon the rela-tive difference between these coefficients, may result in buckling or cracking of the coating durin~ baking if an attempt is made to oxidize a coating which is too thick.
The substrate with applied film is placed on the support slab (or suspended) in a closed tube made from a heat resistant material such as quartz, the ~ ~
whole of which is then inserted into a tube furnace. -By way of example, FIGURE 1 illustrates a quartz tube 1 having single-hole neoprene stoppers 8 inserted in both ends. The substrate 2 with the ap-plied film is mounted on microscope slide 3 which rests on support slab 4. The support slab, microscope slide and substrate with applied film are inserted in ~uartz tube 1 which is then placed in a standard Lindberg tube furnace 5 which has been preheated to a temperature below the melting point of the metal foil substrate. (For aluminum substrates which melt at about 650C, the furnace is preferably preheated to about 525C to 610C. Above this range, problems of differential thermal expansion of the aluminum may be encountered, possibly xesulting in buckling or crack-ing of the substrate coating. At lower temperatures, ,, - ~ _ , .

1~3~SSl correspondingly longer oxidization times are re-quired - which may detract from the commercial suit-ability of the method.) An inert gas flow is maintained at a fixed ra~e with the aid of flowmeter 6 and needle valve regulator 7. Gases which have flowed through quartz tube 1 may be passed through bubbler apparatus 11 to assist in preventing back flow of air into quartz tube 1. Various gases are suitable as the inert gas.
Both purified nitrogen and argon have proven to be acceptable. It is expected that helium would also perform satisfactorily.
The substrate and applied film is baked in the inert atmosphere, thereby driving off the suspend-ing media for the MoS2 particles. After the substrateand applied film has been allowed to reach thermal equilibrium (at which point substantially all of the suspending media should have evaporated), oxygen is admitted to closed.tube 1 and is caused to flow with the aid of the flowmeter 9 and the needle valve regu-lator 10 past the substrate to oxidize the MoS2 par-ticles.
Gas flow rate is adjusted with the aid of flowmeters 6 and 9 and needle valve regulators 7 and 10, such that the flow rate is fast enough to prevent a backflow of air into the tube through the tube gas outlet port~ but also slow enough to prevent cool-ing of the substrate due to the flow of gas past the substrate. If the gas flow rate is too low, an ox-ygen concentration gradient may be set up along the -- ;L-3 --~13~55~

length of ~he .substrate such that more oxygen will diffuse into the coating at the end of the substrate closest to the source of the oxy~en flow than will diffuse into the coating at the end of the substrate farthest from the source of the oxygen flow. The gas flow rate must therefore be adjusted to minimize the effect of any such oxygen concentration gradient.
It is considered that the problem with oxy-gen concentration gradient and the resultant require-ment for careful control over the gas flow rate may be alleviated by adapting the method to the production of a continuous cathode by moving a continuous strip of substrate with applied film past a stationary oxygen source which bathes the moving strip in oxygen for a time period dependent upon the rate at which the strip is moving. The inventors believe that production of cathodes by such a moving strip method may result in an economically viable means for mass production of cathodes.
Use of a vacuum furnace may also alleviate the oxygen concentration gradient problem. If a vacuum furnace is used then the partial pressure of oxygen within the furnace may be monitored to yield a concentration of oxygen eqùivalent to that which would have been required if oxygen in an inert gas atmosphere had been used. A "cold trap" may also be used to remove sulphur dioxide produced during oxidiza-tion of MoS2 in the vacuum furnace.
Where direct conversion from MoS2 to MOO2 or to a mixture of MoS2 and MoO2 is to be achieved, ~3 -- ,;L-4 --careful regulation of oxygen concentration and oxidi-za~ion time is required. For a given average MoS2 par-ticle diameter and a given oxidization time, the maxi-mum allowable concentration of oxygen in the inert atmosphere which will impede the formation of molyb-denum oxides other than MoO2 has been found to be dependent upon temperature and upon the thickness of the film desired to be oxidized. The inventors are not able to provide generalized conclusions respecting the conditions under which the formation of molybdenum oxides other than MO2 will be impeded. Reference should be made to the Examples which follow. of course, in adjusting the concentration of oxygen in combination with the parameters discussed below, care should be taken not to establish an oxygen concentra-tion gradient along the length of the substrate, as mentioned above.
Once a baking temperature is selected, and a corresponding suitable concentration of oxygen in a given inert gas determined, a suitable oxidization time must be determined. The rate of oxidation of MoS2 has been found to vary approximately exponen-tially with temperature and approximately linearly with oxygen concentration (below the maximum allow-able oxygen concentration above which formation of molybdenum oxides other than MOO2 may occur). The oxi-dization time should be selected to be sufficiently long to allow the desired proportion of MoS2 to be converted to MoO2, but sufficiently short to prevent the reaction of MO2 with oxygen to form other molyb-~375S~

denum oxides. ~n appropriate oxidization time maybe determined empirically. For example, several sub-strates with applied films which have been baked for varying lengths of time may be examined through x-ray diffraction analysis to determine the amounts of MOO2 and/or other molybdenum oxides produced. Oxidiza-tion times of a few minutes have been found appropri-ate at higher temperatures (about 550C), while oxi-dization times of several hours have been found to be required at lower temperatures.
By direct conversion, it is possible to pro-duce cathodes in which the cathode-active material is a "mixture" of both MoO2 and MoS2 in ratios which may vary substantially over the entire compositional range (i.e. about 100% MoO2 to about 100~ MoS2). Such cath-odes may be produced by baking the substrate and ap-plied coating for a time sufficient to allow only a selected proportion of MoS2 to be converted to MoO2.
Cathodes containing a "mixture" of MoS2 and MoO2 may not be produced by the "indirect" conversion discussed hereinafter since substantially all of the MoS2 is converted to MoO3 which is then converted to MoO2.
The inventors advise against simply mixing selected proportions of MoS2 particles and MOO2 particles and then adhering the mixed particles onto the substrate in some manner to fabricate a cathode in which the cathode-active material is a "mixture" of both MoS2 and MoO2. The inventore believe that when a cathode containing such a "mixture" is produced by direct con-version, then an MO2 coating forms on the MoS2 par-.,'j~, /S , 113755~

ticles. Thus, individual MoS2 particles are given a metallic coating which improves ele~trical conducti-vity between adjacent particles. If MoS2 particles are simply mixed indiscriminately with MoO2 particles, it is believed that problems of electrical cond~cti-vity may be experienced in the completed cathode.
By way of summary and further explanation, the following procedure has been found acceptable for fabricating by direct conversion a battery cathode which includes MoO2 as a cathode-active material:
MoS2 concentrate is washed in organic solvents and water to remove substantially all traces of organic impurities. Inorganic impuri-ties may also be removed by a leaching process or in any known manner.
The MoS2 concentrate is then mixed with a viscous liquid. The mixture should com-prise approximately equal parts by volume of MoS2 and viscous liquid. Propylene glycol has been found to be an acceptable viscous liquid.
The resulting slurry is applied as a film to a metal substrate. A screening process may be used to yield a film of uniform desired thick-ness. The sùbstrate and applied film may be dried in an oven at 100C for a few minutes to simplify handling. The substrate may be, for example, a piece of aluminum foil. The inventors have used an aluminum foil strip having an area of approximately 20 cm and approximately 20 microns thick as a substrate. In using an aluminum sub-/G
, -- }- 7 --~ 375 strate, the inventors usually apply a film to yield a distribution of up to about 20 mg/cm of MoS2 on the substrate.
The substrate with applied film is then placed directly on a support slab with the coated surface of the substrate away from the support slab. An aluminum slab measuring approxi-mately 12 inches x 2 inches x 1/4 inch may be used as a support. The support and substrate are then placed in a quartz tube such that the substrate with applied film is longitudinally aligned with the tube axis. An inert gas is caused to flow through the tube. Once the tube has been flushed of air (approximately 10 minutes after the inert gas begins to flow), the tube is placed in a standard Lindberg-type tube furnace which has been preheated to the pre-selected baking temperature and the substrate is allowed to reach thermal equilibrium in the furnace. Once the substrate has reached thermal equilibrium, oxygen is added to the inert gas flowing through the tube at a rate governed as described above. The oxygen concentration and a corresponding baking tempera-ture are predetermined as described above to dis-courage formation of molybdenum oxides other than MOO2 during baking. The tube is left in the fur-nace with the gas mixture flowing for an oxidiza-tion time (which has been pre-determined as des-cribed above) which is sufficient to convert a selected proportion, or substantially all of the ~ f _ ~ _ 113755~

MoS2 to ~2' but not long enough to encourage the further conversion of MO2 to other molybdenum oxides~ The oxygen flow is turned off at the end of the oxidization time, the inert gas flow main-tained and the tube is removed from the furnace.
After the tube has cooled (approximately 5 minutes) the inert gas flow is turned off and the completed cathode is removed from the tube.
(b) MoS2 to MoO3 to MOO2 ("indlrect conversion") As indicated above, to produce an MOO2 cath-ode "indirectly" from MoS2 there is first an oxidiza-tion step, then a reduction step.
The oxidization step may be performed by fol-lowing the procedure generally as described for direct conversion. However, since the object of the oxidiza-tion step now is to encourage conversion of the MoS2 to MoO3 and not to MoO2, careful regulation of oxygen concentration and oxidization time is not as critical as it is in the case of direct conversion when the object is to encourage conversion of the MoS2 to MOO2 and not to MoO3.
Thus, to effect the oxidization step, an MoS2 film may be applied to a metal foil substrate and the substrate and applied film then placed on a support slab and inserted into a quartz tube as des-cribed in the case of direct conversion. The tube containing the support slab, substrate and applied film is then placed ir. a standard Lindberg tube furnace which has been preheated (preferably to about 525C to 610C if an aluminum substrate is used), and _ ,1,~ _ ' t .~"~,, - 1137SS~

an oxygen containing atmosphere is then caused to flow through the tube. The tube is left in the furnace until substantially all of the MoS2 has been converted to MoO3 (the substrate coating should be pale yellow or white in color when this has happened).
Then, the reduction step follows.
To effect reduction, the oxygen fl~w is turned off and, preferably, the tube is flushed with an inert gas (e.g. nitrogen) for several minutes before the reducing atmosphere is introduced. Then, a reducing atmosphere such as hydrogen mixed with the inert gas is caused to flow through the tube, the furnace temper-ature having been lowered to a temperature in the neigh-bourhood of 430C to 450C. The substrate is baked in the reducing atmosphere for several hours until substan-tially all of the MoO3 has been reduced to MoO2. The hydrogen flow is then turned off, and the tube removed from the furnace and allowed to cool for approximately 5 minutes before the completed cathode is removed.

EX~MPLES

The following examples are provided to give those skilled in the art a better understanding of the invention:
Example 1 A cathode which included MO2 as the cathode-active material was constructed on a platinum foil strip using direct conversion as follows:

(a) 3 milligrams of a 10% by weight suspension in heavy lubricating oil of MoS2 particles having an average particle diameter of about -- ~ _ - ~13755~l .25 microns was applied as a film to the platinum substrate.
(b) The coated substrate was inserted into a quartz tube through which nitrogen gas was caused to flow at about .8 litres per minute.
(c) The tube was then placed in a Lindberg tube furnace which had been preheated to about 575C. The tube was allowed to reach thermal equilibrium in the furnace.
(d) A mixture of about 0.1 mole percent oxygen in nitrogen was then caused to flow through the tube at about .8 litres per minute for

2 minutes. Then, pure nitrogen was again caused to flow through the tube for a further

3 minutes.
(e) The tube was then removed from the furnace and allowed to cool for about 5 minutes after which time the nitrogen flow was turned off and the completed cathode removed from the tube.
The completed cathode was used to construct a cell in a glass beaker which was sealed with a neoprene stopper. A lithium anode and the prepared cathode were suspended in the beaker from wires fitted through holes drilled into the stopper. The beaker was filled with about 20 cc of a .7M solution of LiBr in propylene ca~bonate which served as the cell electrolyte. An argon atmosphere was introduced into the airtight beaker.
The cell was then discharged and recharged at 200 lo ,;~
, 13~5Sl microamperes. FIGURE 2 is a graph in which the cell voltage discharge and recharge characteristics are plotted versus time.
Example 2 An MOO2 cathode was made using indirect con-version as follows:
(a) A coating of about 1.6 mg/cm MoS2 was applied as a film to a 19 cm2 piece of 20 micron thick aluminum foil.

tb) The substratè with applied film was placed on an aluminum support slab and inserted in a quartz tube through which a pure nitrogen atmosphere was caused to flow. The tube was placed in a Lindberg tube furnace which had been preheated to about 575C, and allowed to reach thermal equilibrium in the furnace.
(c) A gas mixture of about 0.3 mole percent oxygen in nitrogen was then caused to flow through the tube for about 17 minutes. This time was found to be sufficient to convert the approximately 1 micron MoS2 particles to MoO3.
(d) The furnace temperature was then reduced to 440C and a hydrogen atmosphere caused to flow through the tube. The baking was continued for 9 hours before the completed cathode was removed from the furnace and tube.
X-ray diffraction analysis revealed that the substrate was coated with essentially pure MoO2 contain-ing relativqly small trace amounts of molybdenum metal.

~1 _ ,~, _ - ~137551 A cell was constructed as in Example 1 using a 2.5 cm piece of the prepared cathode. Discharge characteristics similar to those of Example 1 (as shown in FIGURE 2) were obtained.
Example 3 A cathode was constructed on a 20 micron thick piece of aluminum foil using direct conversion as follows:
(a) MoS2 powder having an average particle diameter of about 20 microns was mixed in a 1 to 1 volume ratio with propylene glycol and a film of the resulting slurry applied to the aluminum foil substrate.
(b) The substrate with applied film was baked at 580C in an atmosphere containing about 0.4 mole percent oxygen in nitrogen for about 10 minutes to form a cathode containing approximately 20 mole percent MOO2 and approximately 80 mole percent MoS2.
A cell was constructed using two stainless steel flanges separated by a neoprene O-ring sealer.
The anode consisted of a 6 cm sheet of lithium. A
6 cm piece of the prepared cathode (on which had been deposited approximately 43 milligrams of cathode-active material (MOO2 + MoS2)) was used as the cell cathode.
A porous polypropylene separator sheet which had been soaked in a 1 M solution of lithium perchlorate in propylene carbonate was inserted between the anode and the cathode.
The newly constructed cell was conditioned 1~375~1 by initially discharging it at 4 milliamperes to a lower cutoff voltage of about 0.85 volts. During this initial discharge, the cell voltage dropped in about 20 minutes to a plateau of about 1 volt and then de-creased approximately linearly to a~out 0.85 volts in a further 2 hours. The cell thus prepared and conditioned was cycled through 66 discharge-charge cycles at about

4 milliamperes between a minimum voltage of about 0.8i volts and a maximum voltage of about 2.7 volts. FIGURE
3 is a graph which shows the cell discharge-charge characteristic beginning with the fifth discharge.
Alternatively, particulate MoS2 may be con-verted to particulate MOO2 using either direct or in-direct conversion. For example, if indirect conversion is used MoS2 particles may be stirred or tumbled while baking them in an oxygen - containing atmosphere to yield particulate MoO3 and then further stirring or tumbling the MoO3 particles while baking them in a reducing atmosphere to yield particulate MoO2. Then, when it is desired to produce a cathode which comprises MOO2 as a cathode-active material, a suspension of some of the MOO2 particles may be applied as a film to a metallic substrate as described above and then baked in an inert atmosphere to drive off the suspending media for the particles, leaving a coating of MOO2 adherent on the substrate. In the case of direct conversion, MoS2 particles are converted to MOO2 or MoS2 coated with MOO2 while stirring or tumbling in an oxygen-containing atmosphere. The following is an example where direct conversion was used:

-- ~1;375Sl EXAMPLE
(a) MoS2 powder having an average particle diameter of about 20 microns was placed insi~e a quartz tube which was then in-serted into a Lindberg tube furnace.
(b) A mixture of oxygen gas flowing at about 4 c.c./min. and nitrogen gas flowing at about 2 litres/min. was caused to flow through the tube for about one hour dur-in which time the furnace temperature was held at about 550~C. The quartz tube was continually rocked during this time to stir the particles.
(c) The quartz tube was then removed from the furnace and allowed to cool.
(d) A ~ample of the oxidized powder was sus-pended in propylene glycol and applied as a film to an aluminum substrate which was then baked in a nitrogen atmosphere at about 550C for about 15 minutes to yield a 6 cm2 cathode bearing about 30 mg.
of cathode-active material.
(e) The completed cathode was used to construct a cell as in Example 3.
(f) The newly constructed cell was cooled to about 0C. and then conditioned at 0C. by initially discharging it at 1 milliampere to a lower cutoff voltage of about .65 volts. During this initial discharge, the cell voltage dropped to a plateau of about 1 volt and then decreased approximately linearly to about .65 volts.
(g) The cell thus prepared and conditioned was cycled at ambient temperature at about 2 milliamperes between about 1.1 volts and about 2.7 volts.

Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A battery cell, comprising:
(a) a lithium anode:
(b) a non-aqueous electrolyte; and, (c) a cathode having a cathode-active material which comprises molybdenum dioxide.

2. A battery cell, comprising:
(a) a lithium anode;
(b) a non-acqueous electrolyte; and, (c) a cathode having a cathode-active material which comprises molybdenum dioxide and molybdenum disulphide.

3. A battery cell, comprising:
(a) a lithium anode;
(b) a non-aqueous electrolyte; and, (c) a cathode having a cathode-active material which consists essentially of molybdenum disulphide particles coated with molybdenum dioxide.

4. A battery cell as defined in claim 2 or 3 wherein the mole percentage of molybdenum disulphide is relatively small in relation to the mole percentage of molybdenum dioxide.

5. A battery cell as defined in claim 2 or 3 wherein the mole percentage of molybdenum disulphide is relatively large in relation to the mole percentage of molybdenum dioxide.