Cathode materials

Methods for the preparation of polyvinylpyridine and iodine (PVP.nI.sub.2) as cathode materials for electrochemical cells.

DESCRIPTION 
Background of Prior Art 
Batteries, such as those of the lithium/iodine type of example, sometimes 
referred to as solid state cells, make use of a cathode material comprised 
of iodine and an iodine containing charge transfer compound. Charge 
transfer compounds are sometimes referred to as complexes and sometimes as 
donor-acceptor compounds. The iodine in such a cathode reacts 
electrochemically with the lithium anode to provide a voltage output. This 
reaction causes a lithium iodine electrolyte to form in situ between the 
anode and cathode. The charge transfer donor typically used is a 
polyvinylpyridine, (PVP) such as poly-2-vinylpyridine (P2VP) of 
poly-4-vinylpyridine (P4VP). Additional amounts of free iodine i.e., 
excess iodine which is not combined with the charge transfer donor, are 
usually included as part of the cathode material to provide an iodine 
"reservoir" for the battery to draw on during discharge. The additional 
iodine increases the useful life of the battery. 
The polyvinylpyridine-iodine cathode compositions previously used, such as 
the P2VP and/or P4VP based cathodes, have exhibited conductivities which 
degrade severely with the addition of relatively large amounts of iodine 
to the complex. Such amounts of iodine are hereinafter referred to as 
"excess iodine". The degradation in the conductivity of the composition 
has been found to effectively limit the amount of iodine which can be 
included in these compositions without degrading the conductivity of the 
material below a useful level. As a result, the previously available 
polyvinylpyridine cathode materials did not have as high an energy density 
as is theoretically expected from an iodine based system. This fact is 
particularly important for the application of these cathode materials to 
implantable medical devices, e.g., heart pacemakers, for example. 
Copending U.S. patent application Ser. No. 901,506, filed May 1, 1978, 
entitled CATHODE MATERIALS and also assigned to Medtronic, Inc., provides 
excess iodine containing polyvinylpyridine-iodine cathodes, P2VP and/or 
P4VP based, and methods for preparing the same. The cathodes have markedly 
higher conductivity than has been heretofore attained. That patent 
application also discloses the preparation of useful cathode materials 
having much higher iodine content, such as materials having a final mole 
ratio of 20:1 or greater overall iodine to P2VP and/or P4VP donor 
components. These improved materials possess higher energy densities and 
longer useful life. The complete content of that patent application is 
incorporated herein by reference. 
Specifically, aforementioned U.S. patent application Ser. No. 901,506 is 
directed to cathode materials and provides methods of preparing cathode 
materials from P2VP, P4VP or mixtures thereof with varying amounts of 
iodine. As a part of the method it is required that at least a part of the 
preparation take place at temperatures in excess of about 225.degree. C. 
in a sealed container in order to obtain the improved conductivities, 
which are characteristic of the materials disclosed in that application. 
In one form of the methods disclosed in the copending application, 
following preparation of a highly conductive cathode material at elevated 
temperature, excess iodine is then added. The iodine is added at room 
temperature and in amounts to provide a final mole ratio of about 20:1 or 
higher, if desired. For example, a final mole ratio of 40:1 may be 
prepared in this manner. Lesser amounts may also be used. 
In another form of the methods disclosed in the copending application, a 
one-step technique is used to prepare the cathode material, which may have 
a mole ratio of 20:1 or higher, directly by initially adding the desired 
ultimate amount of iodine to the mixture being prepared. In this 
embodiment the desired relative final amounts of P2VP and P4VP donor and 
iodine are simply mixed together and heated to a temperature in excess of 
about 225.degree. C. 
Herein, "mole ratio" is defined in terms of the number of moles (n) of 
iodine (I.sub.2) to the number of gram formula weights of vinylpyridine in 
the initial polymer-donor mixture. For example, a mixture which initially 
contains 508 grams of I.sub.2 and 10.5 grams of PVP would have a mole 
ratio of 20:1 and would be designated as PVP.20I.sub.2. "Mole fraction" is 
defined in an analogous manner as n/n+1, according to the above 
nomenclature. 
For descriptive purposes herein, the term "complex" refers to any single 
phase iodine and donor mixture. The term "cathode material" refers to a 
material composed of a "complex" and may include excess iodine, which may 
be present as a solid phase. 
SUMMARY OF THE INVENTION 
This invention provides a modification of the methods disclosed in the 
aforementioned copending patent application which significantly lowers the 
corrosion rate of these cathode materials. Generally, according to this 
invention, the use of vacuum or inert atmospheres, collectively referred 
to herein as "protective atmospheres", at some time during preparation of 
the cathode materials, has been found to lower their corrosion rate. 
Helium and argon are preferred inert atmospheres.

DESCRIPTION OF PREFERRED EMBODIMENTS 
As is disclosed in the aforementioned copending application, the 
conductivity (measured at 37.degree. C.) of cathode material samples of 
P2VP.3.3I.sub.2 (mole ratio) mixture varies with the heating temperature 
used for its preparation. Heating is accomplished in a sealed container. 
Heating at 175.degree. C. produces a conductivity no higher than about 
4.times.10.sup.-3 reciprocal ohm-cm even for very extended heating 
periods. On the other hand, heating at about 225.degree. C. produces a 
material having a conductivity (at 37.degree. C.) of about 
7.times.10.sup.-3 reciprocal ohm-cm for heating times greater than about 
10 hours. Heating at even higher temperatures produces cathode materials 
having even higher conductivities and less heating time is required to 
obtain improved conductivity as the heating temperature is increased above 
about 225.degree. C. 
Other mole ratios of iodine mixed with P2VP donor behave in a similar 
manner i.e., heating above about 225.degree. C. provides higher 
conductivity, as is also illustrated in the copending application. 
However, the mole ratio should be at least 1:1. Preferred P2VP.nI.sub.2 
cathode materials have a conductivity higher than about 
1.5.times.10.sup.-3 reciprocal ohm-cm and a mole ratio of at least about 
12:1. This is readily accomplished at heating temperatures of about 
225.degree. C. or higher and at mole ratios on the order of 20:1. 
Materials using a P4VP donor component behave similarly to those using a 
P2VP donor component. This is illustrated by the copending application 
which shows the conductivities of 3.3:1 mole ratio cathode materials made 
up from P2VP and P4VP donor materials with four hours reaction time at 
heating temperatures of 150.degree. C. and 320.degree. C. All of the data 
indicates that P2VP and P4VP behave analogously in this regard. 
Mixtures of P2VP and P4VP donor material may also be prepared and used. For 
example, a mixture of equal parts P2VP and P4VP was used to prepare a 
3.3:1 mole ratio cathode material. The material prepared at 320.degree. C. 
for four hours had a conductivity of 1.1.times.10.sup.-2 reciprocal 
ohm-cm. 
High conductivity in the cathode material is necessary because, as already 
pointed out, high additional amounts of iodine added to the material 
degrades its conductivity. By providing a high initial conductivity in the 
material, larger amounts of iodine can be added thereto without degrading 
the final conductivity of the resultant material to a low undesirable 
value. With higher mole ratios, one can expect to maintain a conductivity 
of about 10.sup.-3 reciprocal ohm-cm or better with the above-described 
techniques while also obtaining a much improved deliverable energy density 
than has been heretofore possible. As is disclosed in the copending 
application, a P2VP.20nI.sub.2 cathode material prepared at higher 
temperatures, as described above, and tested in a battery having a lithium 
anode provided about 90% of stoichiometric capacity to a 2.0 Volt cut-off 
at 3uA/cm.sup.2 load. The cathode material was prepared by heating a 
mixture of P2VP.3.3I.sub.2 to 300.degree. C. for about four hours in a 
sealed glass container. Upon cooling, excess iodine was added to the 
material to provide a final mole ratio of P2VP.20I.sub.2. 
There are two ways to incorporate the excess iodine into the material. In 
the first and presently most preferred form, the polyvinylpyridine polymer 
component is mixed with a relatively low amount of iodine, such as 3.3 
mole ratio or less, i.e., enough to merely form a single phase cathode 
material with little or no excess iodine. The mixture is heated in excess 
of about 225.degree. C. for a predetermined period of time, dependent upon 
the temperature selected, to form material of improved conductivity. For 
example, heating a 3.3 mole ratio sample at about 225.degree. 
C.-320.degree. C. for about one hour produces material of improved 
conductivity as is shown in the aforementioned copending application. An 8 
hour reaction time appears to be adequate to assure complete reaction at 
various temperatures above about 225.degree. C. However, longer times may 
be used. An additional amount of iodine may then be added, at any 
convenient temperature i.e., room temperature or elevated, to provide any 
desired excess amount in the final cathode material resulting from this 
preparation. 
As can be seen from the above, highly conductive materials may be prepared 
from P2VP, P4VP or mixtures thereof i.e., P2VP.nI.sub.2 and/or 
P4VP.nI.sub.2 where n (indicative of mole ratio) may range from about 1.0 
to 3.3. A preferred value for n is 3.3 in the case of P2VP and iodine. 
Such a preferred composition will exhibit a conductivity on the order of 
4.times.10.sup.-3 reciprocal ohm-cm or higher. Optionally, additional 
iodine may be added. 
As is noted above, seen from the aforementioned copending application, 
cathode materials may be prepared by heating at 250.degree. C. for about 8 
hours. Upon cooling and measuring the conductivity thereof at 37.degree. 
C., these materials exhibit a conductivity on the order of 10.sup.-2 
reciprocal ohm-cm or greater. If a higher temperature e.g., 320.degree. C. 
is used, the time for heating can be shortened to on the order of an hour 
or so and a 37.degree. C. conductivity on the order of 10.sup.-2 
reciprocal ohm-cm can still be attained or exceeded. The 37.degree. C. 
temperature at which conductivity is measured for samples discussed herein 
was selected arbitrarily. Other temperatures may be used for measuring the 
conductivity of these materials so long as any selected temperature is 
used consistently for purposes of comparison between samples. 
Heating temperatures in excess of 350.degree. C. show no substantial 
increased benefit as to heating time in attaining the high conductivity 
levels as is shown in the copending application. From a practical 
standpoint, heating at temperatures in excess of this level appears to be 
of no practical benefit. P4VP based compounds can be prepared over the 
same temperature range as those of P2VP. 
Upon cooling to room temperature, following the above method of 
preparation, the high conductivity P2VP, P4VP, or mixed P2VP/P4VP cathode 
material will be more or less fluid depending on the amount of iodine 
included therein and the temperature to which they were heated. 
Thus, in order to prepare a high energy density cathode material for 
battery use, it is only necessary to mix an amount of additional iodine 
with a material prepared in the above-described manner. Preferably, the 
iodine is ground into a convenient powder form for this purpose. Elevated 
temperatures may be used for mixing the iodine with the material but are 
not necessary. The amount of additional iodine may be selected to provide 
any desired final mole ratio relative to the P2VP and/or P4VP organic 
constituents. In the case of batteries for implantable medical devices, it 
is preferred that the final mole ratio be at least on the order of 12:1. 
For example, using a P2VP.3.3I.sub.2 material prepared according to the 
above technique, having a conductivity in excess of 10.sup.-2 reciprocal 
ohm-cm and being fluid in form, powdered iodine was added thereto in 
sufficient quantity to provide a material having a final mole ratio of 
about 20:1. The resultant cathode material was of a wet sand-like 
consistency and dark appearance. It was pressed to a density of about 4.7 
g/cc and used in a battery. 
The aforementioned copending application describes a second method of 
preparation in which highly conductive cathode materials are prepared 
ranging over various iodine mole ratios by simply including the desired 
final amount of iodine in the heating container with the polyvinylpyridine 
polymer, sealing the container and heating it to a temperature greater 
than about 225.degree. C. for a predetermined time dependent on the 
selected temperature. 
The table shows the conductivity of several samples of 20:1 mole ratio 
cathode material prepared according to one or the other of the two 
preparation techniques described above. 
The first four cathodes were prepared by the first technique or the 
two-step method using initial mole ratios between 1:1 and 6.2:1 and 
diluting with additional iodine to provide the final 20:1 mole ratio. 
The table also shows a sample prepared according to the second technique, 
sufficient iodine being added initially, prior to heating at reaction 
temperature, to result in a cathode material having a final 20:1 mole 
ratio. As can be seen, all samples had conductivities between 1.2 and 
2.1.times.10.sup.-3 reciprocal ohm-cm. 
TABLE 
______________________________________ 
Conductivity of 
Reaction Temperature Composition* 
Final P2VP . 20I.sub.2 
(Mole Ratio I.sub.2 :P2VP) 
at 37.degree. C. (ohm-cm).sup.-1 
______________________________________ 
1:1 1.25 .times. 10.sup.-3 
2.1:1 1.39 .times. 10.sup.-3 
3.3:1 1.75 .times. 10.sup.-3 
6.2:1 2.05 .times. 10.sup.-3 
20:1 1.56 .times. 10.sup.-3 
______________________________________ 
*Reaction time 4 hours at 320.degree. C. 
As already indicated, it has been determined in accordance with this 
invention that the above described materials may in some instances tend to 
be somewhat corrosive, such as when used with stainless steel and other 
iron base electrochemical cell components. In accordance with this 
invention, it has been discovered that the use of a protective atmosphere 
i.e., a vacuum or inert atmosphere, during preparation of these materials 
results in a material which exhibits significantly lower corrosion rates. 
The above described methods of preparation are merely modified to 
preferably include the establishment of a vacuum or an inert atmosphere in 
the sealed container prior to heating the material to its reaction 
temperature and may include exposure of the material, following its 
preparation, to a vacuum to remove volatiles. The use of vacuum steps both 
before and after heating is preferred. Also, the use of ambient atmosphere 
during heating followed by short-time vacuum removal of unwanted volatiles 
will provide the benefits of this invention. By short-time, something less 
than about one hour is meant at vacuum levels of about 1mm Hg to about 
100mm of Hg. 
The components of the materials and the reaction temperatures and times for 
the methods of preparation are not changed from the aforementioned 
copending application. For example, iodine and P2VP were mixed together in 
the amounts required to form a final 3.3:1 mole ratio. The mixture was 
placed in a glass container which was evacuated to about 1 mm of Hg. The 
container was sealed and the contents heated to 300.degree. C. for 3hours. 
The resultant material provided the following conductivity results: 
18.degree. C.--1.95.times.10.sup.-3 (ohm-cm).sup.-1 
37.degree. C.--7.31.times.10.sup.-3 (ohm-cm).sup.-1 
60.degree. C.--1.83.times.10.sup.-2 (ohm-cm).sup.-1 
whereas it has a corrosion rate of only 8.00.times.10.sup.-4 inches/year as 
compared to 2.00.times.10.sup.-2 inches/year for some of the materials 
described in the copending application. 
As a second example, a 100 gram mixture having a 3.3:1 mole ratio was 
prepared as described in the example immediately above, except that the 
heating temperature was 320.degree. C. and the heating time was 4 hours. 
The resultant fluid had a corrosion rate of 3.0.times.10.sup.-4 
inches/year. Conductivity was: 
18.degree. C.--2.93.times.10.sup.-3 (ohm-cm).sup.-1 
37.degree. C.--1.04.times.10.sup.-2 (ohm-cm).sup.- 
60.degree. C.--2.25.times.10.sup.-2 (ohm-cm).sup.-1 
In a third example, a 3.3 mole ratio mixture was prepared by mixing 
appropriate amounts of iodine and P2VP in air. This mixture was sealed 
into a glass container with the ambient entrapped air and heated at 
320.degree. C. for 4 hours. Following heating, the container was evacuated 
for about 1/2 hour for the removal of unwanted volatiles. The conductivity 
of the resultant material was similar to the second example described 
immediately above and the corrosion rate was 9.3 .times.10.sup.-3 
inches/year. 
As a fourth example, a 3.3:1 mole ratio of iodine and P2VP was prepared by 
placing the materials in a glass container and sealing it with an inert 
argon atmosphere inside. The mixture was heated at 320.degree. C. for 4 
hours. Its conductivity at 37.degree. C. was 8.26.times.10.sup.-3 and its 
corrosion rate was 2.times.10.sup.-4 inches/year. 
A last example was prepared as above, except the mole ratio was 20:1. Its 
corrosion rate was 2.times.10.sup.-3 inches/year. 
Corrosion rates were measured on 304L stainless steel by the technique of 
calorimetry. The heat given off via the corrosion reaction was measured 
and interpreted in terms of a corrosion rate. The heat of corrosion of 
304L stainless steel was calculated from the heats of formation of the 
corrosion products assuming the average composition of the stainless steel 
to be 65%Fe, 20%Cr and 12%Ni and the corrosion products to be FeI.sub.2, 
CrI.sub.2 and NiI.sub.2. 
Examples of PVP which may be used with this invention are shown below. PVP 
from other sources will also be satisfactory for use with the invention. 
P2VP may be synthesized as follows: 
Benzoyl peroxide (2.0 grams) is dissolved in freshly distilled 
2-vinylpyridine (200 grams). Water (400 ml) is added and the mixture is 
purged with nitrogen for 1 hour. With continued purging, the mixture is 
heated at 85.degree. C. with stirring and kept at that temperature for two 
hours. The organic phase will thicken and develop a brown color during 
this time. The mixture is cooled; the aqueous phase is discarded and the 
organic phase is dried overnight at 60.degree. C. in a vacuum oven. The 
residue is ground into fine granules and dried to a constant weight of 
60.degree. C. in the vacuum oven. Yield 162 gm (81%) poly-2-vinylpyridine. 
This product can be expected to provide the following results upon 
analysis by gel permeation chromatography: 
Number-average molecular weight--199,000 
Weight-average molecular weight--555,000 
P2VP was also obtained from the Ionac Chemical Co., Birmingham, Alabama: 
typical weight-average molecular weight--301,000; typical Number-average 
molecular weight --128,000. 
P4VP may be synthesized as follows: 
Freshly distilled 4-vinylpyridine is purged with nitrogen for one hour. The 
4-vinylpyridine is heated with stirring under a continuing nitrogen purge 
to 160.degree. C. and maintained at that temperature for 90 minutes. The 
contents of the reactor will darken and thicken during this time until 
agitation becomes very difficult to maintain. The reaction product is then 
poured warm into a container for storage and tightly sealed. 
The product can be expected to provide the following results upon analysis 
by gel permeation chromatography: 
%volatiles (probably monomer)--34% 
Weight-average molecular weight--6000 (includes monomer). 
P4VP may also be obtained from Polysciences, Inc., identified as #0112. 
Having described the invention, the embodiments thereof in which an 
exclusive property right is claimed are defined in the following claims.