for the Treatment of Certain Metallic Alloys for the Manufacture of Elements for Voltaic Batteries and Caustic Alkalies or their Derivatives.
Year: 1894

page_text: being date of first Foreign Application 7th May, 1894
(in France),
Date of Application (in United Kingdom), 29th Nov., 1894
Complete Specification Left, 28th Aug., 1895-Accepted, 16th Nov.,
1895
PROVISIONAL SPECIFICATION
Process for the Treatment of Certain Metallic Alloys for the
Manufacture of Elements for Voltaic Batteries and Caustic
Alkalies or their Derivatives.
I, LÉON PAUL HULIN, of Modane, (Savoie) France, Civil Engineer do hereby
declare the nature of this invention to be as follows:-
My invention has for its object a process of treating certain metallic alloys
whereby to conjointly produce
(1) Electrodes applicable according to their nature either for primary or
secondary batteries or accumulators.
(2) Caustic alkalies or their derivatives.
The simultaneous obtainment of these commercial results is based on the
employment of a material which I have rendered common to them and also
comprises during manufacture, operations intimately uniting these two results as
will be hereinafter explained.
I employ as the essential material an alloy containing a heavy metal and an
alkali metal or alkali-earth metal of which the oxide is soluble in water.
The heavy metal is that the metal of which it is desired the electrode should be
composed, for example lead, copper &c. The alkali metal is selected according to
the alkali to be produced, potassium, sodium, barium &c.
I preferably employ the alloys obtained by my electrolytic process forming
the subject of another application for Letters Patent dated the 28th day of
November 1894 No. 23117 because of its economical character and because by
employing a chloride of an alkali as the material treated the alkali will be the
final product of the combination of the two processes.
I take an alloy thus selected, melt it out of contact with air and cast it in a
mould of the form of the electrode to be produced. I generally place in the
mould a grid of a metal less fusible than the alkali alloy, either of lead or copper
or it may be of carbon provided with suitable appendages and which serves both
as a support and as an electric conductor. It will be understood that the form of
these electrodes has no connection with the system of manufacture which I claim;
they are generally made in the form of plates, hollow cylinders or rods of various
cross sectional forms.
The general construction of the moulds is likewise independent of the invention,
they being of known kind.
After cooling I remove the casting from the mould and subject it to the second
operation which consists in immersing the moulded article in water preferably cold
or still better in saline or acid solutions as will be hereinafter explained.

page_text: In this manner I obtain at one operation and in an express manner (1) a mass of
spongy metal permeable to electro-chemical action, forming the electrode (2) an
aqueous solution of caustic alkali or alkaline derivative.
When the whole of the alkali metal of the casting has passed into solution
I remove the piece of spongy metal (electrode) which should then be washed and
dried.
A very important advantage of this system of manufacturing electrodes lies in
the intimate union of the alloy with the metallic grid serving as its support.
The alkali metal contained in the alloy in fact effects during the casting the
reduction of the thin layer of oxide which covers the grid and thus brings about
a true weld between the alloy and its support.
After the elimination of the alkali-metal the spongy metal remains united to
the metallic frame. This result conduces to increase the strength as well as
the conductivity of the electrode and in itself alone constitutes an important
improvement.
The complete performance of my process moreover comprises characteristic
operations which I will proceed to describe and which are based on the following
considerations:-
1st. The groups of electrodes employed in secondary and primary batteries
comprise metallic peroxides in their composition.
It is therefore necessary to be able to peroxidize a portion of the electrodes.
2nd. By the reaction of the water upon the castings of alloy on leaving the
mould hydrogen is disengaged from within the mass and the reaction is so vigorous
as to fatigue the spongy matter to such an extent as to cause its disaggregation.
It is therefore necessary to so operate as to avoid this destruction.
3rd. This nascent hydrogen is capable of producing chemical action of a reducing
nature and I have therefore sought to utilize it in this direction.
4th. The chemical action of the alkali metal upon the water generates electrical
energy and this upon an article specially formed to store it; it is therefore
desirable to utilize this electricity and this I do by employing it to peroxidize
electro-chemically those of the electrodes for which peroxidation is requisite.
I will now describe how all these results may be intimately combined in a single
operation. I will suppose the electrodes to be of flat form with contact tangs and
intended for use in accumulators of the ordinary kind.
I place the castings after removal from the mould and cooling in a series of
troughs and alternately between carbon plates of the same size; the plates of the
a common conductor so as
same kind in each trough being connected together by
to connect the poles of like sign and form an electro-chemical couple. Similarly
I set up with plates of spongy metal a second series of similar couples and
establish electrical communication between the two series in such manner that the
group of plates or alloy of the first series, communicates with the group of carbon
plates of the second series and reciprocally the spongy plates of the second series
I thus obtain a complete
are connected with the carbon plates of the first series.
circuit comprising a source of electricity (plates of alloy) and an electrolytic
apparatus (spongy plates to be peroxidized). Around the plates of alkali alloy of
the first series of troughs I pour a cold solution of alkaline nitrate for example.
The said troughs are if necessary combined with a refrigerating arrangement of
any kind to prevent rise of temperature and so moderate the progress of the
reaction. Around the spongy plates which are to be peroxidized (second series
of troughs) I pour a dilute solution of sulphuric acid.
The alkali alloy then decomposes the water in which it is immersed producing
alkali and electrical energy; the nascent bydrogen is absorbed (on contact with
the resulting spongy metal) by the oxygen of the alkaline nitrate and this
combination similarly produces a further quantity of electrical energy; on the
other band as the hydrogen does not appear in the gaseous state it leaves the
spongy metal of the electrode perfectly coherent and finally the alkaline nitrate is
converted by the hydrogen into soda and ammonia, that is to say into alkalis in

page_text: conformity with the object of the operation.
The electric current is wholly
utilized in the second series of troughs to peroxidize the spongy plates in the
known manner. Thus this absorption of the hydrogen furnishes three results
intimately connected with the formation of the electrodes and the production of
alkalies viz. coherence of the spongy metal, electrical energy and conversion of the
alkaline nitrate into two free alkalis.
Instead of alkaline nitrate I may employ any other reagent capable of serving the
same purposes and I would indicate more particularly a solution of sulphurous acid
which would yield on these conditions as direct derivative a solution of an alkaline
hydro-sulphite.
I may also by employing sodium nitrate in regulated quantity and by suitably
limiting the time of the reaction, obtain as direct derivative along with the alkali,
a solution of sodium nitrate. To obtain electrodes of spongy lead and peroxide
I employ any alkali alloy but I preferably employ (and this forms a distinguishing
feature of the present invention) an alloy of lead and barium as being advan-
tageous of treatment and giving excellent results from all the points of view which
have been mentioned. With the alloy of copper and sodium or other alkali metal
I prepare electrodes cast around wire gauze or perforated sheet metal, which after
being peroxidized may be employed with advantage for primary elements, such, for
example, as zinc-potash, oxide of copper. This oxidation may as regards the
copper be effected in the air at a high temperature.
A. M. & WM. CLARK,
53 Chancery Lane, London, Chartered Patent Agents.
Process for the Treatment of Certain Metallic Alloys for the
Manufacture of Elements for Voltaic Batteries and Caustic
Alkalies or their Derivatives.
I, LEON PAUL HULIN, of Modane, (Savoie), France, Civil 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:-
My invention has for its object a process of treating certain metallic alloys
whereby to conjointly produce :-
(1) Electrodes applicable, according to their nature, either for primary or
secondary batteries or accumulators or for use in electrolytic operations
generally;
(2) Caustic alkalies or their derivatives.
The simultaneous obtainment of these commercial results is based on the
employment of a material which I have rendered common to them, and also
comprises during manufacture, operations intimately uniting these two results as
will be hereinafter explained.
I employ as the essential material an alloy containing a heavy metal and an
alkali metal or alkali earth metal of which the oxide is soluble in water. The
heavy metal is the metal of which it is desired the electrode should be composed,
for example lead, copper, etc. The alkali metal or alkali earth metal is selected
according to the alkali or alkali earth to be produced, potassium, sodium,
barium, etc.
I preferably employ the alloys obtained by my electrolytic process forming the
subject of another application for Letters Patent dated the 28th day of November
1894, No. 23,117; because of its economical character and because by employing

page_text: a chloride of an alkali as the material treated, the alkali will be the final product
of the combination of the two processes. I take an alloy thus selected, melt it out
of contact with air, and cast it in a mould of the form of the electrode to be
produced. I generally place in the mould a grid of a metal less fusible than the
alkali alloy and which may either be of lead or copper or it may be of carbon
provided with suitable appendages and which serves both as a support and as an
electric conductor.
It is to be understood that the form of these electrodes has no connection with
the system of manufacture which I claim; they are generally made in the form of
plates, hollow cylinders, or rods of various cross-sectional forms. The general
construction of the moulds is likewise independent of the invention, they being of
known kind.
After cooling, I remove the casting from the mould and subject it to the second
operation, which consists in immersing the moulded article in water preferably
cold, or still better in saline or acid solutions, as will be hereinafter explained. In
this manner I obtain at one operation and in an express manner (1) a mass of
spongy metal permeable to electro-chemical action, forming the electro le, (2) an
aqueous solution of caustic alkali or alkaline derivative. When the whole of the
alkali metal of the casting has passed into solution, I remove the piece of spongy
metal (electrode) which should then be washed and dried.
A very important advantage of this system of manufacturing electrodes lies in
the intimate union of the alloy with the metallic grid serving as its support. The
alkali metal contained in the alloy in fact effects during the casting the reduction
of the thin layer of oxide which covers the grid and thus brings about a true weld
between the alloy and its support. After the elimination of the alkali metal, the
spongy metal remains united to the metallic frame. This result conduces to
increase the strength as well as the conductivity of the electrode and in itself alone
constitutes an important improvement.
The complete performance of my process, moreover, comprises characteristic
operations which I will proceed to describe and which are based on the following
considerations:-
1st. The group of electrodes employed in secondary and primary batteries
comprise metallic peroxides in their composition. It is therefore necessary to be
able to peroxidize a portion of the electrodes;
2nd. By the reaction of the water upon the castings of alloy on leaving the
mould, hydrogen is disengaged from within the mass and the reaction is so vigorous
as to fatigue the spongy matter to such an extent as to cause its disaggregation.
It is therefore necessary to so operate as to avoid this destruction.
I have discovered that in order to obtain this important result there should be
added to the water a soluble oxygenated compound capable of absorbing the whole
or a portion of the hydrogen, so as to arrest or moderate its evolution, and thus
ensure the preservation of the metal of the electrode in a spongy and coherent
state. The oxygenated compounds which I thus employ with success for preventing
the destruction of the spongy inetal during the elimination of the alkali metal by
the water are, particularly, nitrates, sulphurous acid, and sulphites in solution. The
spongy metal forming the electrode remains remarkably strong or coherent, in
place and in shape, when the alkali metal is eliminated in those solutions.
3rd. The nascent hydrogen is capable of producing chemical action of a reducing
nature and I have therefore sought to utilize it for obtaining at same time useful
bye-products.
4th. The chemical action of the alkali metal upon the water generates electrical
energy and this takes effect upon an article specially formed to store it; the
electricity being utilized by employing it to peroxidize electro-chemically those of
the electrodes for which peroxidation is requisite.
I will now describe how all these results may be intimately combined in a single
operation. I will suppose the electrodes to be of flat form with contact tangs and
intended for use in accumulators of the ordinary kind. I place the castings after

page_text: removal from the mould and cooling, in a series of troughs and alternately between
carbon plates of the same size, the plates of the same kind in each trough being
connected together by a common conductor so as to connect the poles of like sign
and form an electro-chemical couple. Similarly I set up with plates of spongy
metal a second series of similar couples and establish electrical communication
between the two series in such manner that the group of plates of alloy of the
first series communicates with the group of carbon plates of the second series and
reciprocally the spongy plates of the second series are connected with the carbon
plates of the first series. I thus obtain a complete circuit comprising a source of
electricity (plates of alloy) and an electrolytic apparatus (spongy plates to be
peroxidized). Around the plates of alkali alloy of the first series of troughs, I pour
a cold solution of alkaline nitrate for example. The said troughs are if necessary
combined with a refrigerating arrangement of any kind to prevent rise of
Around the spongy
temperature and so moderate the progress of the reaction.
plates which are to be peroxidized (second series of troughs) I pour a dilute
solution of sulphuric acid. The alkali alloy then decomposes the water in which it
is immersed producing alkali and electrical energy; the nascent hydrogen is
absorbed (on contact with the resulting spongy metal) by the oxygen of the
alkaline nitrate and this combination similarly produces a further quantity of
electrical energy; on the other hand as the hydrogen does not appear in the
gaseous state or appearing much more slowly it leaves the spongy metal of the
electrode perfectly coherent and finally the alkaline nitrate is converted by
the hydrogen into soda and ammonia, that is to say into alkalies in conformity with
the object of the operation. The electric current is wholly utilized in the second
Thus this
series of troughs to peroxidize the spongy plates in the known manner.
absorption of the hydrogen furnishes three results intimately connected with the
formation of the electrodes and the production of alkalies, viz. :-coherence of the
spongy metal, electrical energy, and conversion of the alkaline nitrate into two free
alkalies.
Instead of alkaline nitrate I may employ any other re-agent capable of serving
the same purposes, that is to say preventing or lessening the disengagement of gas.
I have indicated previously more particularly a solution of sulphurous acid or of
an alkaline sulphite or bi-sulphite which would yield on these conditions as direct
derivative a solution of an alkaline hydro-sulphite. This important product is thus
obtained by a novel process and by a novel reaction. I may also by employing
sodium nitrate in regulated quantity and by suitably limiting the time of the
reaction, obtain as direct derivative along with the alkali, a solution of sodium
nitrite. To obtain electrodes of spongy lead and peroxide I employ any alkali
alloy, but I preferably employ (and this forms a distinguishing feature of the
present invention) an alloy of lead and barium as being advantageous of treat-
ment and giving excellent results from all the points of view which have been
mentioned. With the alloy of copper and sodium or other alkali metal, I prepare
by the same processes, electrodes cast around wire gauze or perforated sheet
metal suitable for accumulators employing spongy copper or which after being
peroxidized may be employed with advantage for primary elements, such for
example as zinc-potash, oxide of copper. This oxidation may as regards the
copper be effected in the air at a high temperature.
My process naturally applies to the preparation by casting of spongy or porous
metals in any form, for all the uses for which porous metals in an agglomerated
state are employed such as filter plates or cylinders.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is:-
1st. The simultaneous and combined manufacture of electrodes for primary or
secondary batteries and caustic alkalies or their derivatives, which consists in
operating with an alloy (composed of the metal of which the electrode is to be

page_text: formed and of an alkali metal) which is cast in a fused state in a mould of the form
of the electrode and which is then treated with water for producing at once the
active spongy metal which forms the electrode and a solution of caustic alkali.
2nd. In the operation of treatment with water, as specified in Claim 1, the
addition to the water of a chemical agent capable of absorbing sufficient nascent
hydrogen, in order to thus avoid the mechanical destruction of the spongy metal
which would ensue from the too violent disengagement of bubbles of hydrogen
within the metal.
3rd. The utilization of the whole of the electric current produced in the chemical
actions hereinbefore described, more particularly for the electro-chemical peroxida-
tion of the spongy metal obtained in said operations.
4th. The utilization of the chemical and reductive actions produced during the
elemination of the alkali metal, as herein described, for the preparation of caustic
alkalies or their derivatives by the employment of suitable substances such as
alkaline nitrates, sulphurous acid, and sulphites, which are transformed into
useful bye-products after having ensured the preservation and cohesion of the
spongy metal.
5th. The application of the above processes for the production of any articles or
apparatus composed of spongy metal in the forin of a compound body having the
necessary physical cohesion such as filter plates or cylinders.
111
100
A. M. & WM. CLARK,
53, Chancery Lane, London, Chartered Patent Agents.