Improvements in Galvanic Batteries and in Electrolytic Baths.
Year: 1888

page_text: Improvements in Galvanic Batteries and in Electrolytic Baths.
We, ISAIAH LEWIS ROBERTS, a citizen of the United States, residing at No. 1
Herkimer Street, in the City of Brooklyn, State of New York, United States of
America, Chemist, and HENRY LEFFERT BREVOORT, a citizen of the United States,
residing at No. 36 Brevoort Place in the City of Brooklyn, State of New York,
United States of America, Mechanical Engineer, do hereby declare the nature of our
invention for IMPROVEMENTS IN GALVANIC BATTERIES AND IN ELECTROLYTIC BATHS,
and in what manner the same is to be performed, to be practically described and
ascertained in and by the following statement:
Heretofore where it has been desired to use two different liquids in the cells of a
Galvanic Battery, porous partitions of earthenware have been employed to separate the
liquids from each other.
To accomplish the separation only, a non-porous partition would have been
preferable, but such a partition would have been useless because it would have cut
off the electrolytic liquids or solutions from contact with each other. This contact has
heretofore been secured by having the partition porous, so that the liquids, penetrating
the pores of the partition, could form lines or chains of electrolytic molecules, through
which electrolytic action or energy could be transmitted. The solid portion of the
porous partition of course offers an absolute resistance to the transfer of electric action
which is transmitted solely by the electrolysis of the liquid or liquids held in the
pores. To reduce the total resistance of the partition, it was therefore desirable or
necessary to have its porosity very great.
Any porous body will however allow or even promote the transfusion of liquids
through it, and therefore such transfusion always and at all times took place where
porous partitions were used and was a necessary, though undesirable, result of their
constitution and mode of action.
In other words the porous partition was itself impotent as a means of transmitting
the electric force, and only acted as a framework to hold the molecules of the
electrolytic liquid or liquids, which transmitted the electric force by their successive
decompositions and re-combinations. The electrolytic liquids however by reason of
their liquid character tended to diffuse and mingle, and this tendency was restrained
by the porous body only to a limited degree.

page_text: To illustrate this, if a solution of sulphate of copper be placed outside an ordinary
porous cup and sulphate of zine on the inside, in a few hours or perhaps in a day, a
large portion of the sulphate of copper will have intermixed with the salphate of zinc,
and a large portion of the sulphate of zinc will have passed through the porous cup
into the sulphate of copper section. This intermixing of the fluids will of course rain
the battery by occasioning "local action."
We make the diaphragm or partition of the battery of a material which is
practically non-porous but with electrolytic properties, so that whether the battery
be on an open circuit or closed circuit, the liquid as such on one side of the partition
will not intermix or intermingle with the liquid on the other side of the partition, or
only to a very limited extent, but when the circuit is closed and the battery is called
upon to give a current of electricity, chemical action can and will take place through
the partition.
In carrying out our invention, we construct the partition or diaphragm either
partially or wholly of a gelatinous or jelly like material which is non-porous but
which contains moisture as one of its characteristic elements.
Thus the partition may be made of starch, preferably boiled in a strong brine of
some salt of an alkali, such as chloride of sodium or a salt of zinc, and the gelatinous
or jelly-like mass so produced may be confined between walls of cloth or other suitable
material to form the diaphragm or partition of the battery cell.
Instead of the starch we may use boiled flour, say rice flour, wheat flour or in fact
the gelatinous substance obtained from any grain or plant. The materials which are
the least soluble are to be preferred. The partition may also be made, but not to such
great advantage, of dough, of flour and water, which may be left unboiled and may be
confined between the sustaining walls.
The thickness of the gelatinous or jelly-like mass forming the partition should be
anywhere from a quarter of an inch upwards, varying with the size of the battery
used, though it may be of more or less thickness. The gelatinous material may be
introduced into a thickness of cloth or felt by being caused to enter and close the
pores thereof to form the non-porous partition, and in this case the two retaining
walls of cloth would not be necessary. In all cases we prefer to use a salt in the
gelatinous material, as it increases the electrolytic properties of the partition.
The action of our diaphragm or partition we believe to be explainable as follows:-
The diaphragm or partition is a non-porous substantially solid homogeneous wall
whose particles while sufficiently solid and compact to maintain their own positions
and so prevent for practical purposes any transmission of fluids through them, are yet
themselves able to act as electrolytes and suffer such decompositions and recom-
binations as are essential to the electrolytic transmission of electric force. In other
words we have in our partition combined in the one substance the solid properties of
the earthenware and the electrolytic properties of the liquid; or, we may say that we
have made the electrolytes solid and the partition electrolytic.
When the jelly-like or gelatinous mass is held between walls, it is advantageous to
stir up with it a filamentous binding material such as hair, fur, asbestos, or fibres of
cotton. This binding material is best added when the mass is being boiled. Enough
of this should be used to bind the material together and avoid cracks and the like in
drying. One pound of starch and six pounds of water, two pounds of chloride of
sodium, and two ounces of cotton fibre may be stirred and boiled together until
cooked, with satisfactory results. Cooking is accomplished when the starch granules
are broken. We may boil with the starch the salt which is to form the basis of the
solution on the zinc side of the battery. Thus if the sulphate of copper is added on
one side and the sulphate of zinc on the other side, we may boil with the starch a
solution of sulphate of zinc. If sulphate of copper is used on one side and chloride of
sodium on the other, we prefer to boil with the substance to form the partition,
chloride of sodium, but to these we do not limit ourselves in any way, as sulphate of
zine would do in the majority of cases, though we prefer chloride of sodium. It is
intended to use in this battery sulphate of copper and a plate of copper on one side
and sulphate of zinc on the other side of the partition, but other materials may be

page_text: used. Weak acids can also be used on either side to increase the conductivity of the
solution or as an excitant.
The accompanying drawings show, as an example, one mode of carrying out our
invention.
Figure 1 is a plan of a cell complete.
Figure 2 is a vertical section on the line ex, figure 1, and
Figure 3 is a vertical section taken at right angles to figure 2.
A is the cell. We have shown here a cell composed of two wooden boxes placed
one within the other, with a layer of asphalt and rosin between. We do not however
confine ourselves to this peculiar style of cell as any other style may be used without
departing from the principles of the invention.
B are two wooden frames, over which is stretched a cloth or canvas C as indicated.
These frames B are fitted to the interior of the cell and are secured in said cell at a
short distance apart and with the canvas covered sides facing each other, and the
space between the canvas sides is completely filled, as at D, with any one of the
materials herein indicated, such as a mixture of boiled starch and cotton fibre, for
instance. Care must be taken not to leave any empty spaces between the canvas, so
as to positively prevent leakage or transfusion of the liquids used in the cell.
When the cell and of course the frame B are of considerable size, we prefer to
introduce the intermediate cross bars b which form a support for the canvas to prevent
it from bulging outward when gelatinous or jelly like material is being filled in or at
any subsequent period.
We wish it to be understood that we do not limit ourselves however to the form of
supports shown as other constructions may be used and for small cells supports may
be dispensed with.
The gelatinous or jelly like material may be used to form the partition or diaphragm
by supporting it with a wall of cloth into the pores of which it has been caused to
enter or between two supporting walls of stretched textile fabric such as loosely woven
cotton goods or the like or in any of the ways herein described for the support of the
gelatinous substance.
We may also use a gelatinous or jelly like substance obtained from albuminous
material. The albuminous material may be obtained from either animal or vegetable
sources, such as the white of egg for instance and should be boiled, cooked or
otherwise treated to make the albumen of the necessary gelatinous or jelly like
character for the purpose.
Some salt of an alkáli or alkaline earth should be
combined with the substance of the albumen to increase the electrolytic properties of
the partition or diaphragm. If the albumen be boiled in water, for instance, the
water should be made strong brine by dissolving in it table salt, zinc sulphate or some
salt of an alkali or alkaline earth. We prefer to stir in the material a filamentous
binding material, such as cotton, fur, wool, flax or asbestos. The gelatinous or jelly
like material thus obtained may be used to form the partition or diaphragm by
supporting it in a wall of cloth or between two supporting walls of stretched textile
fabric such as loosely woven cotton goods or the like or as in any of the ways herein
described.
We may also use saponified substances which are treated so that they form some
kind of a jelly or gelatinous mass which is insoluble in the fluid used in the battery.
The substance thus formed may be used alone or in combination with a suitable holder
or support. We proceed as follows:
In say six pounds of water, preferably hot, we dissolve say four pounds of bar-soap
and while the water is still lot we plunge into it an ordinary earthenware porous cup
preferably. A felt bag or a piece of closely fulled felt will answer our purpose, but
we prefer a porous cup made very porous. We leave the cup or other holder in the
solution till no more air will come out of it, which can be told by the bubbles. This
will require from half an hour to two hours more or less. We then take our holder
from the solution and plunge it into a bath of preferably muriatic acid, though other
acids or salts such as bichromate of soda or potash, or salammoniac can be used. A
weak or strong solution of the acid can be used, if weaker the soaking must be longer,

page_text: if stronger, a shorter period of treatment will suffice. With a muriatic acid bath
at 20° Beaume half an hours soaking will suffice for an ordinary porous cup, though
we prefer a longer period. With the salts, a saturated solution or at least a strong
solution is to be preferred. Any acid will do which will unite with the alkaline base
of the saponified material, and any substance will do for a soap which can be
saponified. Any salt may be used that will cause the precipitation of the soap. We
may mix with the saponifiable mass or with the saponified substance such substance
as paraffine, rosin and the gums generally. Such substances as seem to combine with the
saponified or saponifiable mass, as does paraffine, will do to mix with the soap either
before or after saponification, and we find them advantageous. We find that it is
advantageous to mix with the solution of soap silicate of soda which can be dissolved
in the water used to dissolve the soap. Any desired quantity can be so used, and the
proportions can be varied to suit the desires of the person making the mixture. The
silicate of soda is useful in making the resulting mass more glutinous. After the
saturated holder has been treated as before described in an acid it is ready for use as
a separating partition or diaphragm in an electric battery to separate two liquids.
These liquids may be sesqui-chloride of iron on one side, and table salt dissolved in
water on the other. Acids can be used on one side of the separating partition if
desired.
The holder may be saturated with the saponified material and its final treatment
with an acid or a salt may be accomplished by the battery fluids themselves after the
partition cup or diaphragm has been placed in the battery itself. We can take
stearic acid and rub it into the pores or interstices of a suitable holder and treat it with
an acid or salt as above described and obtained a useful result.
Another way of carrying our invention into effect is as follows: Our method now
to be described consists in making the gelatinous or jelly like partitions or diaphragms
with the aid of mineral substances from which, materials of gelatinous character can
be produced. We preferably saturate or impregnate a suitable support or holder with
these mineral gelatinous substances, employing as a support or holder preferably a
porous cup, so that the pores of the separating diaphragm are closed by the mineral
gelatine.
We prefer cup shaped diaphragms or partitions, because they do not require to
be fastened to the walls or bottom of the vessel which is to be divided into compart-
ments. Thus a porous cup of baked earthenware we find convenient. Such a cup
may be of any well known form, such for instance as that illustrated in the accom-
panying drawing, in which :-
Figure 4 is a perspective view of the cup or separating diaphragm A: and
Figure 5 is a vertical section of a two cell battery B containing the cup or
separating diaphragm A, but without the electrodes.
It is known in practical chemistry that certain mineral substances can be turned
into what are known as gelatinous substances. Thus silicate of soda or of potash
can, by treatment with an acid or metallic salt, be turned into a gelatinous mass.
So also the salts of tin, such as the stannates by treatment with an acid the
chlorides by treatment with an alkali, thus in both cases precipitating in gelatinous
form the stannic or silicic oxides. The salts of aluminium may also be gelatinized
by treatment with an alkali. The various mineral substances which can be gelatinized
are numerous, and works on chemistry will give an account of them. We need not
therefore mention them at length.
As one method of carrying our invention into effect, we take a porous cup,
preferably of baked earthenware, very porous, and we saturate this by soaking it,
say for two to ten hours, the longer the better, in an aqueous solution of silicate of
soda or potash. The solution should be just thin enough to enable it to penetrate
the pores of the cup. Heat may be used to hasten the saturation of the cup. When
the cup is thoroughly saturated, we dip it, say for an hour, in muriatic acid, which
we prefer, or the salts of a metal, such as chloride of iron. These substances
cause the silicate to deposit silica in the shape of a gelatinous mass in the pores of
the holder. When this is accomplished the separating partition is formed by the

page_text: walls of the porous cup, having its pores closed with the mineral gelatinous mass-
It is evid that this can be done with all of the various substances which formn what
we call mineral gelatinous masses.
When we use a porous holder, preferably of earthenware, the pores of which are
filled with the gelatinous silicate of soda or potash, the jelly like material cannot be
for any length of time exposed to the air and still retain its jelly like character, as it
will decrepitate in the pores of the holder, become crystalline and will merely act to
obstruct the pores, but will not possess the electrolithic properties which it is essential
that the jelly like mass should have.
To enable us to treat the porous holders with the mineral gelatinized material, and
to keep the same after treatment until such time as it is desirable to use them, we
make use of the following method of treatment: To enable our cups, partitions or
diaphragms to be shipped and kept after the above treatment we subject them immediately
after their removal from the acid or salt bath to a bath made of a saturated solution of
Chloride of Magnesium preferably through other deliquescent salts can be used such as
Chloride of Calcium. In this bath, the cup, partition or diaphragm should be kept two or
three days and when they are removed they can be kept in the ordinary atmosphere
indefinitely without the gelatinized silicate losing its valuable property in and about the
pores of the holders. In this way partitions or cups can be made commercial articles
and can be manufactured shipped and made in large quantities and kept for use as
desired. The Chloride of Magnesium may be applied in various ways to the cup,
for example it may be sprinkled thereon either in a crystallized condition as a
powder or if dissolved in water it may be applied with a brush in successive
applications but a bath as above described is the easiest and best method to be
employed.
We do not claim filling up the pores of the porous holder with crystals or
crystallized masses, but we only claim the jelly like or gelatinous masses such as we
bave described in the above specification.
Another means of carrying out our invention is shown in the accompanying
drawings.
In Figure 6, the cell which may be square or round is shown at A; and the cup is
shown at B made in any of the ways described in the specification, but preferably of
baked earthenware and very porous, and having the pores preferably filled with
silicate of soda properly gelatinized, so as to give to the cup the physical characteristics
herein described.
The elements are shown at C and D, with their conducting wires x and y leading
from them. The two fluids a and b are shown as separated by the cup B.
In Figure 8 a cell A is shown having in it the elements C and D each surrounded
by its appropriate solution a and b. The solution or liquids are separated by the
partition, diaphragm or separating wall B which is cemented at all points to the wall
of the cell A as shown at d, the separating partition like the cup in Figures 6 and 7,
must have the physical structure or density to be capable of separating two fluids as
described, yet possessing the electrolytic quality essential to the chemical or electro-
lytic action of the fluids through it without physical transfusion in the ordinary
sense.
Any mere change of form may be made in the cup or partition, or in the arrange-
ment of the cell and elements as desired without departing from the essence of our
invention..
An electrolytic bath as contemplated in our specification consists of a containing
vessel or cell such as we have shown having its interior separated into two
compartments by a cup, partition or diaphragmn made in accordance with the description
contained in this specification and having on one side or in one compartment a solution
of zinc sulphate and a zinc element, and on the other side a solution of sulphate of
copper and a copper element. The current should be so passed through the electrolytic
bath, that the zinc will be deposited upon the cathode and the copper dissolved
from the copper anode, thus transferring the acid radical from the sulphate of' zinc

page_text: compartment and making it unite with the copper of the sulphate of copper compart-
ment, the partition, cup or diaphragm preventing the two liquids as such from
commingling with each other.
We are aware that prior to the date of our present application it has been proposed
to successively impregnate porous pots, partitions and the like with suitable chemical
agents for the purpose of obtaining a deposit within the pores thereof and that in
particular such pots or partitions have been impregnated with sodium silicate and an
acid, the deposited gelatinous silica being then reduced to the pulverulent form, we
therefore make no claim for such treatment.
Having now particularly described and ascertained the nature of our said
inventions and in what manner the same is to be performed, we declare that what
we claim is :-
1. A separating diaphragm or partition for an electric battery composed partially or
wholly of a jelly-like or gelatinous material.
2. A separating partition or diaphragm for an electric battery having
closed by gelatinous material.
its pores
3. A two-fluid electric battery having a separating diaphragm or partition of
gelatinous or jelly like material obtained from vegetable growths.
4. A separating diaphragm or partition for an electric battery, composed partially
or wholly of gelatinous material combined with a salt, as and for the purpose set
forth.
5. A separating diaphragm or partition for an electric battery, having its pores
closed by a gelatinous material containing a salt, substantially as described.
6. In an electric battery, a separating diaphragm or partition of gelatinous or jelly
like material combined with supporting devices, substantially as described.
7. In an electric battery, a separating diaphragm or partition of gelatinous material,
combined with a supporting sheet or sheets of textile material.
8. In an electric battery, a separating diaphragm or partition of gelatinous material
obtained from boiled vegetable growths, substantially as described.
9. A separating diaphragm or partition for an electric battery, partially or wholly
of starch, substantially as described.
10. A separating diaphragm or partition for an electric battery of starch supported
in position by a sheet or sheets of textile fibrous materials, substantially as described.
11. A separating diaphragm or partition for an electric battery of gelatinous
material combined with binding or holding material in the form of filaments.
12. A separating partition or diaphragm for an electric battery consisting of
earthenware having its pores closed with gelatinous material, substantially as
described.
13. A separating partition or diaphragm for an electric battery consisting of
earthenware having its pores closed with gelatinized silicate of soda or potash.
14. The process of treating porous cups, diaphragms or partitions which consists
in closing their pores with a substance which can be gelatinized, gelatinizing the
..substance in an arm or holder and treating the same with a deliquescent salt
substantially as described.
15. The process of treating porous cups, diaphragms or partitions, which consists
of subjecting them to a bath of silicate of soda or potash gelatizing the silicate of
soda or potash with an acid and preserving the gelatinized material permanently
by treatment with a deliquescent salt, substantially as described..
16. The process of treating porous cups, diaphragms or partitions, which consists
in gelatinizing the material within and about the pores of the holder and treating
the same with a deliquescent salt, as described.
17. The process of treating porous cups, diaphragms or partitions, which consists
in closing their pores with a substance that can be gelatinized, gelatinizing the
substances in and about the pores of the holder and treating the same with Chloride
of Magnesium, substantially as described.
A...

page_text: 18. The process of treating porous cups, diaphragms or partitions, which consists,
first in closing their pores with silicate of soda or potash, gelatinizing the same
and treating the cup with a solution of chloride of magnesium, substantially as
described.
19. The process of treating porous cups, diaphragms or partitions, which consists
in closing the pores in the partition with silicate of soda or potash, gelatinizing
the silicate of soda or potash absorbed in and about the pores of the holder by
treatment with an acid, and subsequently treating the gelatinized material with
chloride of magnesium substantially as described.
20. The process of treating porous cups, diaphragms or partitions, which consists,
first, in treating them to a bath of silicate of soda or potash dissolved in water;
then treating them in a bath of sulphuric acid, to gelatinize the silicate; finally,
treating the cup, diaphragm or partition in a bath consisting of a saturated solution
of chloride of magnesium, substantially as described.
21. A diaphragm or partition for an electric battery, partially or wholly of a
gelatinous or jelly like substance obtained from albuminous materials.
22. A diaphragm or partition for an electric battery, partially or wholly of a
gelatinous or jelly like substance obtained from albuminous materials and combined
with a salt, substantially as described.
23. A separating partition or diaphragm for an electric battery composed
partially or wholly of a gelatinous or jelly like substance made of insoluble
saponified material.
.
24. A separating partition or diaphragm for an electric battery composed of a
porous substance impregnated with insoluble saponified material.
25. A separating partition or diaphragm for an electric battery composed of
earthenware having its pores closed within soluble saponified material.
26. As a new article of manufacture, a cup partition or diaphragm, for use in an
electric battery or electrolytic bath, composed of a porous substance having its pores
closed with gelatinous material.
27. As a new article of manufacture, a cup, partition or diaphragm for use in an
electric battery or electrolytic bath, composed of gelatinous material, combines with a
supporting sheet or sheets of textile material.
28. As a new article of manufacture, a cup, partition, or diaphragm, for use in an
electric battery or electrolytic bath, composed of textile or fibrous materials impregnated
with a gelatinous material.
Dated this 18th day of Danamba 1000
HUGHES, ELI & HUGHES,
76, Chancery Lane, London, W.C.,
Agents for the Applicants.