Improvements in Electrical Batteries.
Year: 1896

page_text: Improvements in Electrical Batteries.
I, CHARLES EDOUARD O'KEENAN, of 168 Rue de Greuelle, Paris, France,
Engineer, do hereby declare the nature of this invention to be as follows:-
It is well known that the negative plates of accumulators (such as the F.S.V.
battery) get heated when they are exposed to the air after a full charge of
current.
That phenomenon is due to the production of suboxyde of lead caused by the
oxygen of the air. If a lead plate thus oxydised is put into a diluted solution of
sulphuric acid for a few hours, the suboxyde decomposes itself into metallic leat
on the one part, and protoxyde of lead on the other, forming with the acid,
sulphate of lead imbedded in the lead plates, exactly as happens in an ordinary
discharge of accumulators. If we take one of these plates so prepared, and place
it in a proper tank containing a solution of sulphate of zinc opposite a zinc plate,
of about the same size, we will then have a cell-lead, sulphate of lead-
sulphate of zinc, zine which gives a current as constant as the Daniell cell.
There is an absolute difference between this battery and Becquerel's and others
sulphate of lead batteries where the depolarisation is very imperfect, and the
internal resistance very great: this difference can be explained by the different
molecular state of the sulphate and by the presence of reduced metallic lead in
the whole material, as has been explained here above. The lead and zinc plates
can be put together in the same elements in as great a number as required and
the aspect is exactly that of an accumulator, excepting that the peroxydised plate
is replaced by a zinc plate, and the acidulated water by sulphate of zine. When
the current lowers after a long discharge the only thing necessary is to expose
again the lead plates to atmospheric air in order to provoke a new oxydation, then
to place these plates in acidulated water as before for a few hours; have the
plates put into water to do away with the free acid, and finally place them again
in the elements, causing a new discharge to be produced and so on.
A very suitable and cheap arrangement is to take rectangular tin tanks for cells,
putting in at each end a piece of wood in which a certain number of grooves has
been made, in which the lead and zinc plates can slide easily without touching
each other.
A suitable thing to do is to make a permanent contact between the tin tank
and the zinc plates of each cell, so as to prevent the oxydisation of the tin tanks as
is done by the galvanisation of the iron of the telegraph wires with zinc, which
forms a galvanic cell, iron-zinc. I find by any experiments that the E.M.F. of
the battery is not at all diminished by that disposition which gives very good
results.
Other materials can be used for the tanks; glass, ebonite, pottery, wood
whether lined with lead or otherwise. As the battery works, the sulphate of zinc
increases in density and consequently should be brought back to the proper
dilution by a suitable supply of water."

page_text: This I obtain automatically so as to insure the best conductivity of the liquid
in all the elements of the battery by the simple use of a tap.
To the bottom of each element is affixed a tube in the shape of a tea pot spout,
its upper outlet being a little lower than the upper part of the element. The
addition of fresh liquid in the upper part of the battery causes the outflow of an
equivalent quantity of the lower stratum of the liquid by the tube. The fresh
liquid is distributed in all the elements by a trough of the same length as the
battery and on which are affixed as many a flow pipes as there are elements. A
second trough receives the dense liquid from the outlet pipes and is provided with
two exit tubes, one being an overflow or a waste pipe, so as to insure a constant
level. The other tube at the bottom of the second trough, is connected to two
other tubes. The liquid in the tube issuing from the trough is dense sulphate of
zinc. Another tube contains pure water flowing when wanted from a tap. A
third tube corresponding with the two former contains diluted sulphate of zinc
at the proper density, furnishing fresh liquid for battery. This diluted solution
being regulated by the different levels of the liquids, in an inverse ratio of their
densities in the three tubes.
The lead plates to be kept in good working order should be treated as follows.
A stock of plates larger in number than wanted for the battery, should be kept
in hand and each day or at other regular intervals a certain number of these
plates should be taken out and others put in their stead.
On taking out the plates, they should be dropped into acidulated water (sulphate
acid) and left in until bubbles have ceased rising; the second operation is to
leave them in the air for oxydation after which they are plunged a second time
in acidulated water and finally rinsed in pure water.
N.B.By the addition of carbonate of soda to the water bath, the small
quantity of free acid which mechanically or through capillarity might adhere to
the plates will be more completely neutralized. Although the first acidulated bath
be not absolutely necessary, it is to be recommended.
The zine may be amalgamated but this is not necessary, ordinary zine answer-
ing nearly as well as sulphate of zinc has no action on the zinc plates as long as
the circuit is open.
The charge of the lead plates may be reduced to the acidulated bath without
exposition to air, but this would take more time.
The electric "formation" of lead plates can be obtained in the battery itself,
if lead plates with chloride of lead "pastilles" are used. When the reduction is
complete the plates can be used as ordinary and well formed plates; this would
reduce the prime cost of the plates.
Dated this 28th day of November 1896.
L. DEVINAGE,
Agent for Applicant.
Improvements in Electrical Batteries.
I, CHARLES EDOUARD O'KEENAN, of 168 Rue de Grenelle, Paris, France,
Engineer, do hereby declare the nature of this invention and in what manner the
same is to be performed to be particularly described and ascertained in and by the
following statement: -
It is well known that the negative plates of accumulators (such as the F.S.V.
battery) get heated when they are exposed to the air after a full charge of
Current

page_text: That phenomenon is due to the production of suboxyde of lead caused by the
oxygen of the air. If a lead plate thus oxydised is put into a diluted solution of
sulphuric acid for a few hours, the suboxyde decomposes itself into metallic lead
on the one part, and protoxyde of lead on the other, forming with the acid,
sulphate of lead imbedded in the lead plates, exactly as happens in an ordinary
discharge of accumulators. If we take one of these plates so prepared, and place
it in a proper tank containing a solution of sulphate of zinc opposite a zinc plate,
of about the same size, we will then have a cell:-lead, sulphate of lead-
sulphate of zine, zinc-which gives a current as constant as the Daniell cell.
There is an absolute difference between this battery and Becquerel's and others
sulphate of lead batteries where the depolarisation is very imperfect, and the
internal resistance very great: this difference can be explained by the different
molecular state of the sulphate and by the presence of reduced metallic lead in
the whole material, as has been explained here above. The lead and zinc plates
can be put together in the same elements in as great a number as required and
the aspect is exactly that of an accumulator, excepting that the peroxydised plate
is replaced by a zinc plate, and the acidulated water by sulphate of zinc. When
the current lowers after a long discharge the only thing necessary is to expose
again the lead plates to atmospheric air in order to provoke a new oxydation, then
to place these plates in acidulated water as before for a few hours: have the
plates put into water to do away with the free acid, and finally place them again
in the elements, causing a new discharge to be produced and so on.
A very suitable and cheap arrangement is to take rectangular tin tanks S (see
drawing) for cells putting in at each end a piece of wood K, L in which a certain
number of grooves has been made, in which the lead and zine plates can slide
easily without touching each other.
A suitable thing to do is to make a permanent contact between the tin tank
and the zine plates of each cell so as to prevent the oxydisation of the tin tanks as
is done by the galvanisation of the iron of the telegraphic wires with zine, which
forms a galvanic cell, iron-zine. I find by my experiments that the E.M.F. of
the battery is not at all diminished by that disposition which gives very good
results.
Other materials can be used for the tanks; glass, ebonite, pottery, wood
whether lined with lead or otherwise. As the battery works, the sulphate of zinc
increases in density and consequently should be brought back to the proper
dilution by a suitable supply of water.
This I obtain automatically so as to insure the best conductivity of the liquid
in all the elements of the battery by the simple use of a tap. In the annexed
drawing is shown the arrangement of the automatic supply device.
A
To the bottom of each element is affixed a tube 1) in the shape of a tea-pot spout,
its upper outlet being a little lower than the upper part of the elements. The
addition of fresh liquid in the upper part of the battery causes the outflow of an
equivalent quantity of the lower stratum of the liquid by the tube. The fresh
liquid is distributed in all the elements by a trough A of the same length as the
battery, and on which are affixed as many a flow pipes as there are elements.
second trough B receives the dense liquid from the outlet pipes and is provided
with two exit tubes, one C being an over flow or a waste pipe so as to insure a
constant level. The other tube E at the bottom of the trough B, is connected to
two other tubes F, G. The liquid in the tubes E F G is dense sulphate of zinc
issuing from the trough B. The tube H contains pure water flowing when wanted
from a tap R. The tube I contains diluted sulphate of zinc at the proper density
furnishing fresh liquid for the battery. This diluted solution being regulated
by the different levels of the liquids, in an inverse ratio of their densities in the
tubes.
The level of the water in the tube H, serves as a manometer showing both the
density of the diluted sulphate of zinc, in the tube I, and that of the denser
sulphate of zine which occupies the tubes E F G. A double scale to the right

page_text: and to the left of the tube H, showing the respective densities, allows to regulate
the proper densities of the liquids; these densities being regulated at will by the
height of the tubes.
The lead plates to be kept in good working order should be treated as follows:
A stock of plates larger in number than wanted for the battery, should be kept
in hand and each day or at other regular intervals a certain number of these
plates should be taken out and others put in their stead.
On taking out the plates, they should be dropped into acidulated water
(sulphuric acid) and left in until bubbles have ceased rising; the second operation
is to leave them in the air for oxidation after which they are plunged a second
time in acidulated water and finally rinsed in pure water.
N.B. By the addition of carbonate of soda to the water bath, the small
quantity of free acid which mechanically or through capillarity might adhere
to the plates will be more completely neutralized. Although the first acidulated
bath be not absolutely necessary, it is to be recommended.
The zinc may be amalgamated but this is not necessary, ordinary zinc answer-
ing nearly as well as sulphate of zinc has no action on the zinc plates as long as
the circuit is open.
The oxydation process of the lead plates may be reduced to the acidulated bath.
without exposition to air, but this would take more time.
The electric oxydation of lead plates can be obtained in the battery itself, if
lead plates with chloride of lead "pastilles" are used, the electric current
decomposing the chloride of lead thus producing an oxydation of the lead plates
and afterwards sulphate of lead by the reaction of the chloric gas on the sulphate
of zinc.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is
1. An electrical battery, in which the costs of materials used up is strictly in
accordance with theory, and in which the oxygen of the air is a gratuitous agent
of depolarisation, distinguished by the use of lead plates previously oxydised and
afterwards treated with sulphuric acid, in connection with zinc plates and
sulphate of zinc.
2. The formation of the lead plates in the battery itself without having to be
formed beforehand as for accumulators, thus producing a great economy in their
cost, by using chloride of lead pastilles.
3. The obtaining of a liquid of a given density for supplying electric batteries
proceeding from two, or more different liquids of different densities adducted by
tubes in which the equilibrium is in inverse ratio of their densities.
4. An improved electrical battery substantially as described.
Dated this 27th day of twout 1807
L. DUVINAGE,
Agent for Applicant.