Improvements in and relating to and in the Manufacture of Electric Secondary Cells.
Year: 1890

page_text: Date of Application, 24th Feb., 1890
Complete Specification Left, 24th Nov., 1890-Accepted, 31st Jan., 1891
PROVISIONAL SPECIFICATION.
Improvements in and relating to and in the Manufacture of Electric
Secondary Cells.
We ARTHUR MARIE FRANCOIS LAURENT-CELY, of 59 Rue de Provence,
Paris, in the Republic of France, and ILLIUS AUGUSTUS TIMMIS, of No. 2 Great
George Street, Westminster, London, S.W., England, Civil Engineer, do hereby
declare the nature of this invention to be as follows:-
The objects of our invention are to produce electrical plates for use in secondary
batteries i.e. positive (or anode) and negative (or cathode) plates which have much
less density and much more storage capacity than any previously made or
described.
The density of our anodes (cellular peroxide of lead) is only 45 to 5 as against a
density of 7 to 9 in the best previously described plates of ordinary peroxide of
lead while the density of our cathodes (cellular lead) is only 3 to 3.5 as against a
density of 6 to 8 in spongy lead.
Again we are able to store 35 to 40 ampère hours per kilo. of active material in
our cells as against 25 to 28 ampère hours in the best previously made or described
cells. And the rate of charge and discharge which we employ is nearly double
that used heretofore.
In the manufacture of the above plates anodes and cathodes we use the following
means and processes.
We melt chloride of lead (which any one can do as this is common property) and
then we add as much as 25 % of pure metallic zinc. The heat in the furnace
(which is by preference a closed one so as to exclude the air as much as possible)
we prefer to have as high as 550° C.--this is a most important feature. The fused
mixture is then run into a receiver and we find it an important feature to make this
receiver sufficiently large to enable the impurities to fall to the bottom and so that
the fused body forms a store of heat.
The vessel which holds the molten mixture is either lined with or made in onc
piece of refractory material or more than one piece and we find it convenient to run
some ordinary lead which protects the bottom of the receiver from the attacks of
the fused body.
Metallic lead is heavier than the mixture. The mixture is then poured into
suitable moulds as hereinafter described and cast into any required forms.
The pastiles (or other forms) are then taken from the moulds and are treated
as follows:-after being washed in a cold concentrated solution of hydrochloric
acid.
The washing of the pastiles in concentrated hydrochloric acid is effected to
destroy any metallic oxides which may be in the pastiles as without this in the
course of forming the plates the sulphuric acid causes soluble sulphates to be formed
and the pastiles disintegrate but we would have it very distinctly understood (as it
18 one of the main features in our invention) that by our process we do not make and
almost entirely prevent the making of metallic oxides. And further by way of
explanation chloride of lead contains no hydrate but chloride of zinc does contain
hydrate and consequently a fused mixture which contains the two chlorides of lead
and zinc contains chloride of lead, chloride of zinc, oxide of lead and oxide of zinc.
And this mixture or combination when treated by sulphuric acid causes the
formation of sulphate of lead and more especially sulphate of zinc which are most
destructible to the plates.
On the other hand if metallic zinc which contains no hydrate, is mixed with fused
or melted chloride of lead a pure compound of chloride of lead and chloride of zinc

page_text: is obtained which is clear of the oxides of these metals. This is a most important
and quite new invention.
The negative pastiles are then washed in pure water and afterwards dried (we
find 120° C. a convenient heat). They are then placed in moulds and spaced and
when the moulds are closed pure lead with 5% to 7% antimony is run in and
forms a framework and also a tang which is used as hereinafter described. The
heat requisite to melt the antimonious lead (say about 350° C.) is considerably less
than that employed to melt the mixture which forms the pastiles. When the
antimonious lead framework is cast round the pastiles the latter have grooves in
them very often in fact we prefer to make them in this way so that the metallic
framework in these grooves acts as an additional support and conductor.
These moulds are lined with asbestos packing which is a most important feature.
These negative plates are now put into suitable boxes with zinc plates. Each set
coupled and then the two sets short circuited the solution being pure cold water
with a few drops of hydrochloric acid. This operation ceases when heat ceases
to be given off and when the active material is soft and perfect. It is now
cellular lead with a density of 3 to 3.5. The plates are then washed in pure cold
water.
The positive pastiles are placed on zinc plates in pure cold water with a little
hydrochloric acid till they are thoroughly transformed into metallic cellular lead
and are then washed in cold water.
They are then heated at a moderate heat in contact with air which is increased
up to 300° C. when the pastiles become cellular litharge with a density of 5 which
is about one half the density of any other active material.
We do not use any hot water or hot solutions or an electric current to produce
the pastiles of cellular lead and cellular litharge.
The fusion and reduction of chloride of lead is not new but is common property
but the addition of metallic zinc is new and the consequent formation of a mixture
free from hydrate which enables us to make low density pastiles which have about
double the capacity of any heretofore made.
The heat applied to the positive pastiles is far greater than ever before tried.
These pastiles are placed in moulds with asbestos packing and a framework of
antimonious lead cast round them as above described.
The and + plates are now put in lead lined or earthenware, glass or other
suitable boxes and coupled up and charged with an electric current of 2 ampères
p. kilo. of lead plates. This is about double the amount used before this.
The arrangement of coupling we believe is quite new. The lead tang allows a
rod to be placed in a slot from below and any one or more plates to be removed.
A rod is threaded and has nuts on it (and washers preferably) to make good
contacts.
We do not bind ourselves to the exact ingredients named but to them or their
known equivalent.
COMPLETE SPECIFICATION.
Improvements in and relating to and in the Manufacture of Electrio
Secondary Cells.
We, ARTHUR MARIE FRANCOIS LAURENT-CELY, of 59, Rue de Provence,
Paris, in the Republic of France, and ILLIUS AUGUSTUS TIMMI8, of No. 2, Great
George Street, Westminster, London, S.W., England, 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 :-
The objects of our invention are to produce electrical plates for use in secondary

page_text: Datteries .e. positive (or anode) and negative (or cathode) plates which have
much less density and much more storage capacity than any previously made or
described.
The density of our anodes (cellular peroxide of lead) is only 4.5 to 5 as against a
density of 7 to 9 in the best previously described plates of ordinary peroxide of lead
while the density of our cathodes (cellular lead) is only 3 to 3.5 as against a density
of 6 to 8 in spongy lead.
Again we are able to store 35 to 40 ampère hours per kilo. of active material in
our cells as against 25 to 28 ampère hours in the best previously made or described
cells, and the rate of charge and discharge which we employ is nearly double that
used heretofore.
In the manufacture of the above plates anodes and cathodes we use the following
means and processes.
We melt chloride of lead (which any one can do as the melting of lead and other
chlorides see Maxwell Lytes expired Patent 136382 is common property) and then
we add as much as 25% of pure metallic zinc. The heat in the furnace (which is
by preference a closed one so as to exclude the air as much as possible) we prefer to
have as high as 550° C.-this is a most important feature. The fused mixture is
then run in a receiver and we find it an important feature to make this receiver
sufficiently large to enable the impurities to fall to the bottom and so that the fused
body forms a store of heat.
The vessel which holds the molten mixture is either lined with or made in one
piece of refractory material or more than one piece and we find it convenient to run
some ordinary lead which protects the bottom of the receiver from the attacks of
the fused body. Metallic lead is heavier than the mixture. The mixture is then
poured into suitable moulds as hereinafter described and cast into any required
forms.
The pastiles (or other forms) are then taken from the moulds and are treated as
follows after being washed in a cold concentrated solution of hydrochloric acid.
The washing of the pastiles in concentrated hydrochloric acid is effected to
destroy any metallic oxides which may be in the pastiles as without this in the
course of forming the plates the sulphuric acid used causes soluble sulphates to be
formed and the pastiles disintegrate but we would have it very distinctly understood
(as it is one of the main features in our invention) that by our process we do not
make and almost entirely prevent the making of metallic oxides. And further by
way of explanation chloride of lead contains no hydrate but chloride of zinc does
contain hydrate and consequently a fused mixture which contains the two chlorides
of lead and zinc contains chloride of lead chloride of zinc, oxide of lead and oxide
of zinc and this mixture or combination when treated by sulphuric acid causes the
formation of sulphate of lead and more especially sulphate of zinc which are most
destructive to the plates. And on the other hand if metallic zinc which contains
no hydrate is mixed with fused or melted chloride of lead a pure compound of
chloride of lead and chloride of zinc is obtained which is clear of the oxides of these
metals. This is a most important and quite new invention.
The negative pastiles are then washed in pure water and afterwards dried (we
find 120° C. a convenient heat). They are then placed in moulds and spaced and
when the moulds are closed pure lead with 5% to 7% antimony is run in and forms
a framework and also a tang which is used as hereinafter described. The heat
requisite to melt the antimonious lead (say about 350° C.) is considerably less than
that employed to melt the mixture which forms the pastiles. When the antimonious
lead framework is cast round the pastiles the latter have grooves in them very often,
in fact we prefer to make them in this way so that the metallic framework in these
grooves acts as an additional support and conductor.
These moulds are lined with asbestos packing which is a most important feature.
These negative plates are now put into suitable boxes with zinc plates. Each set
coupled and then the two sets short circuited the solution being pure cold water
with a few drops of hydrochloric acid. This operation ceases when heat ceases to

page_text: be given off and when the active material is soft and perfect. It is now cellular
lead with a density of 3 to 3.5. The plates are then washed in pure cold
water.
The positive pastiles are placed on zinc plates in pure cold water with a little
hydrochloric acid till they are thoroughly transformed into metallic cellular lead
and are then washed in cold water.
They are then heated at a moderate heat in contact with air which is increased
up to 300° C. when the pastiles become cellular litharge with a density of 5 which
is about one half the density of any other active material.
We do not use any hot water or hot solutions or an electric current to produce
the pastiles of cellular lead and cellular litharge.
The fusion and reduction of chloride of lead is not new but is common property.
But the addition of metallic zinc is new and the consequent formation of a mixture
free from hydrate which enables us to make low density pastiles which have about
double the capacity of any heretofore made.
The heat applied to the positive pastiles is far greater than ever before tried.
These pastiles are placed in moulds with asbestos packing and a framework of
antimonious lead cast round them as above described.
The and plates are now put in lead lined or earthenware, glass or other
suitable boxes and coupled up and charged with an electric current of 2 ampères
per kilo. of lead plates. This is about double the amount used before this.
The arrangement of coupling we believe is quite new. The lead tang allows a
rod to be placed in a slot from below and any one or more plates to be removed.
A rod is threaded and has nuts on it (and washers preferably) to make good
contacts.
We do not bind ourselves to the exact ingredients named but to them or their
known equivalent.
The drawings herewith coupled with the following description will make our
invention to be more readily understood.
The melting furnace practically a closed one shown in transverse section in Fig. 1
and in longitudinal section in Fig. 2 consists of a furnace having several stories A. A
of a cast iron pan B provided with a sole or flagstone of refractory material. This
pan is covered with removable flagstones C. on the top of which we place cast iron
plates D forming a flue.
The hot gases of combustion pass first under the cast iron pan and then into the
flue C. D without ever communicating with the inside D. After leaving flue C. D
they enter the chimney E.
There are three doors arranged on the outside of the melting furnace. The
first F. is for charging in the mixture of chloride of lead and metallic zinc it has
an extension formed by a dead plate G under which the hot gases of combustion
pass in the beginning of the operation. The chloride of lead fuses on this dead
plate and falls then into the pan. The metallic zinc is then added and the mixture
is removed by means of a cast iron ladle introduced through the second door H
called the casting door. We may use the equivalent of metallic zinc.
A third door I or stirring up door is used to stir up the mixture whilst it is in the
molten state.
At each of these issues there are arranged flues J. J. which collect the fumes
or vapours. These flues unite into a single one of conical shape opening into a
condensation chamber.
Under the pan there is a flagging K of refractory bricks inclined on both sides so
as to form channels in the middle for the purpose of collecting the molten mixture
in case of accident and prevent it falling into the fire. It is very desirable for the
reasons hereinafter appearing to exclude air as much as possible from the mixture
and the above form of furnace enables this to be done more completely than
any other.
After having taken some of the molten mixture by means of the cast iron ladle,
it is run into a hinged cast iron mould A' (Figs. 3. 4 and 5) provided internally

page_text: with cells or any snape.
2. y is the mnge. vens perm
form being given to the pastiles. We show a. b. c. d &c. a series of pastiles of
varied forms.
The next stage consists in washing the pastiles in concentrated hydrochloric
acid. Although we effect the fusion in a closed vessel it is impossible to entirely
avoid the entrance of air through the furnace door and consequently to prevent the
formation of oxy-chlorides in a small degree. The zinc and lead oxides which are
formed must therefore be eliminated.
To effect this we arrange the pastiles (Figs. 6 and 7) on leaden trays A' A' A'
provided with holes permitting easy circulation of the liquid, and with pro-
jections a' a' a' so as to leave between them a sufficient space to prevent the
crushing of the pastiles.
These trays are piled up in any number in wooden vats B' B' lined with lead.
These vats are provided at their lower part with a hole Gin which a tap made of
stoneware or other material not affected by chemicals is fitted. The vat is filled
up with concentrated hydrochloric acid. In this acid any oxides are transformed
into chlorides and the operation is continued until the pastiles contain nothing but
pure chloride of lead.
The vat is then emptied by means of the stone tap and a circulation of water
established for the purpose of removing the excess of hydrochloric acid retained by
the plates.
The two aforesaid operations apply equally to the pastiles which are to form
the positive plates and to those used in the manufacture of the negative plates.
After the second operation the pastiles are divided into two groops: the
positive pastiles and the negative ones. Each group undergoes a different
treatment.
Firstly with respect to the positive pastiles by means of reduction and transfor-
mation into litharge.
The positive pastiles cleaned and washed as has been explained above_are
subjected to a reduction process to be first of all turned into cellular lead. This
reduction is effected by an electro-chemical method (Figs. 8 and 9) by means of
zinc plates d³d separated by lead blocks ees and piled up in a vat D³ lined with
lead. This vat is filled up with water in which the chloride of zinc resulting from
the electro chemical action is dissolved. It is provided with a stoneware tap,
or of any other material not affected by chemicals for the purpose of emptying the
liquid.
After the reduction has been effected in these conditions the positive pastiles are
deprived of all the chlorine which entered into their previous composition. There
remains now nothing but pure cellular lead. The pastiles are then taken into a
stove heated to a temperature ranging between 250° and 300° C. (say 480° to
570° Fah.). Under the oxidising influence of hot air, their transformation into
cellular litharge is effected.
The next stage consists in casting a frame of antimonious lead round the pastile.
The casting of this frame is effected both round the positive pastiles of cellular
litharge and round the negative one of chloride of lead not yet reduced. By the
same means and with the same mould as we are now going to describe.
It consists essentially (Figs. 10 to 17) of two cast iron frames A* A* jointed
together by means of a hinge B*. It can swing round a segment C by means of
trunnions D. Each hollow frame is alround and internally provided with a
hollow EE which correspond to the projection with which the frame of anti-
monious lead must be provided. It is besides lined with asbestos millboard of a
thickness sufficient to form a slightly elastic surface. A platen F* of cast iron
keeps this asbestos millboard in position and permits of any degree of pressure
being imparted by means of the nuts ff. The pressure on the two platens is
obtained by means of six cam levers G. To cast a frame the mould is placed
horizontally and opened at right angles. A template H* which is an exact

page_text: counterpart of the spaces left between and alround the pastiles is laid on the
lower platen (Figs. 15. 16 and 17). It is provided with four projections
which enter holes in the platen and serve to insure the exact position of the
pastiles. The pastiles are placed in the open parts of the template so that spaces
of uniform size are therefore left between the pastiles. The template is removed
by means of handles K without disturbing the pastiles. The upper platen is
lowered and the tightening cam levers are operated. The pastiles are thus pressed
between the pieces of asbestos millboard and cannot be shifted. The mould being
then brought into a vertical position antimonious lead is run through the opening L
The molten metal fills up the spaces left between the pastiles and around the
platens. The pastiles are therefore connected firmly by means of a framework of
lead. The mould being brought back into its horizontal position is opened, the
framework is withdrawn and it is sufficient to let the leaders M M drop to obtain
the accumulator plate. Secondly with respect to the negative pastiles. These
are now provided with a framework of antimonious lead and then it remains only
to reduce them into cellular lead. The plates being still in the state of chloride
of lead, their reduction is effected in the same manner as in the case of the positive
plates, that is by means of an electrolytic bath in a vat containing the plates to be
reduced and zinc plates.
Finally we have thus obtained positive plates consisting of pastiles of cellular
litharge and on the other hand negative plates of pure cellular lead; the pastiles
in either kind of plate being strongly connected with one another by means of a
framework of antimonious lead.
There remains only to group both kinds of plates so as to form them electrically
by the ordinary means.
Having now particularly described and ascertained the nature of our said
invention and in what manner the same is to be performed we declare that what
we claim is :-
First The process of manufacture of positive plates for secondary batteries by
the combined succession of the following operations by means of fusion of the
chloride of lead, addition of metallic zinc, casting into pastiles washing of the
pastiles in concentrated hydrochloric acid, reduction and transformation into litharge
and casting of a framework of antimonious lead between and around the pastiles
substantially as described.
Secondly- -The process of manufacture of negative plates for secondary batteries
by the combined succession of the following operations by means of fusion of the
chloride of lead, addition of metallic zinc casting into pastiles washing of the
pastiles in concentrated hydrochloric acid casting around them a framework of
antimonious lead and reducing them to cellular lead substantially as described.
Thirdly-The arrangement of the melting furnace for fusing chloride of lead
the said furnace containing several stories for the reception of the fuel charging
door casting door and stirring door flues collecting and conducting the fumes into
a condensation chamber substantially as shown in Figs. 1 and 2.
:-
Fourthly The construction and use of moulds for the casting of pastiles of
any form for the construction of secondary cells substantially as shown in Figs. 4
and 5.
:-
Fifthly The arrangement of vats with plates of zinc separated by lead blocks
for effecting the reduction of the pastiles substantially as specified and shown in
Figs. 8 and 9.
Sixthly-The use of asbestos linings to the moulds when casting a framework
round the pastiles substantially as described.
Seventhly-Casting a framework round the pastiles of antimonious lead which
melts at a lower temperature than that of the fused mixture substantially as
described.
:-
Eighthly The use of metallic lead for the purpose of protecting the lining of

page_text: the furnace which being heavier than the fused mixture protects the hearth and
casing from the action of the chlorides substantially as described.
Dated this Twenty-fourth day of November 1890.
ARTHUR MARIE FRANÇOIS LAURENT-CÈLY.
ILLIUS AUGUSTUS TIMMIS.