Plates without Support, Entirely Made of Active Material, for Voltaic Batteries.
Year: 1886

page_text: Date of Application, 6th July, 1886.
Complete Left, 6th May, 1887.
Complete Accepted, 7th June, 1887.
PROVISIONAL SPECIFICATION.
Plates without Support, Entirely Made of Active Material, for
Voltaic Batteries.
I, EMILE ANDREOLI, Journalist, 62 Loughborough Park Brixton Surrey do hereby
declare the nature of this invention to be as follows:-
Secondary batteries heretofore have generally been made by passing a current
through sheets of lead, until the lead has acquired a chemical porosity or by coating
with a paste of minium and litharge a perforated sheet of lead or any other support,
on which the oxides are compressed mechanically.
This invention relates chiefly to the production by means of chemical and
metallurgical methods of dense homogeneous, conductive and coherent plates, blocks,
cylinders and rods which I convert afterwards into negative and positive electrodes for
secondary and primary batteries, each of which plates being a solid mass of activo
material without support of any kind, i.e. consisting entirely on one side of porous
lead or other metal, and on the other of its Peroxide.
My invention relates therefore to a novel method for utilization of metals or metallic
salts for manufacturing plates for voltaic batteries, and according to the qualities I
desire to impart to such plates, viz. to the use they are intended for, I make different
alloys and alter the respective proportions of these components.
In carrying out this invention, I mix substances which I prepare chemically or
otherwise, and I fuse them in an ordinary crucible, and the molten alloy having been
cast, it is electrolytically, brought to a porous or spongy state and formed. If
the agents or re-agents I employ for effecting the composition of such alloys, their
decomposition and transformation into a source of electricity are such as are known
to and used by chemists and metallurgists, I insist nevertheless on this feature as a
novelty of my invention, that without any support of any kind I construct solid plates,

page_text: entirely made of active substance, by chemically agglomerating certain materials, cast
them afterwards in moulds, and by forming them electrolytically, I change the nature
of the above mentioned materials, without pressure whatever, which destroys the
regularity, so to speak, of the honey combed cells of the porous metal, the cohesion of
the molecules and their conductibility, as well as it affects their capacity for absorption
of gases.
I do not confine myself to one metallic alloy, but having found that several metals,
oxides, sulphides chromates etc. can be successfully employed, I include in my method
all the suitable alloys, which after having been cast in a mould, can be converted into
a porous or spongy plate on one side and a peroxide plate on the other. Such plates
are easy to make, they are strong, they do not disintegrate or break and as they
contain more active substance than any other plate of another system, they must be
superior for capacity and efficiency to all the known plates of Secondary batteries.
To give an illustration, I will now mention a few substances 1 can combine to make
a concrete mass of peroxide of lead or of any other metal, used in the electrolytic
tank as the anode, and in the battery as the negative, and of
porous or spongy lead or
other metal, to be the cathode in the electrolytic tank and the positive plate in the
battery.
.
In my choice of metals and chemicals to produce alloys which require porosity I
am guided by experience and by scientific principles and laws which allow me to
produce different kinds of crystals, their texture having the appearance, according to
the materials mixed with iron, lead or other metal fused to form the alloy, either of a
fibrous texture or of small fine needles or of the fineness or coarsness of grain,
similar to the one of steel and of cast iron.
When such plates have been electrolytically treated in a solution which does not
attack lead, but solely the articles with which it had been combined in the crucible, its
appearance has been molecularly modified and transformed and the plates, cylinders,
blocks or rods want simply drying after a short electrolysis and a careful washing in
distilled or rain water, they are formed and charged within a comparetively very short
time.
If I take carbonate of lead and add 5 per cent. at the maximum of Chloride of
Ammonium or Sodium, and about 4 per cent. Iron filings, Tin or Zinc I obtain a
fusible alloy, which treated afterwards by electrolysis and washed in certain liquids,
and after the elimination of the iron, zinc or tin, a plate of pure metallic lead in a
spongy state is obtained.
Similar results are produced with chloride of lead and iron. Chlorine in its
combination with lead and iron or zinc has a tendency to crystallize them. There is
always a portion of chlorine which remains occluded in the pores of the alloy and I
get rid of it, first by washing in hot water and by passing a current in it, because
chlorides are decomposed by electricity. I wash once more the spongy lead, and in
order to be certain that it will be free from all trace of chlorine, I may add to the
water a substance which absorbs chlorine; after a little time, I rapidly withdraw
the plates and place them in a trough where they can be formed and charged by a
strong electric current.
I will now rapidly enumerate some other alloys which I may employ. Phosphate
of lead combines readily with chloride of lead; protoxide of lead, heated with various
metallic oxides, forms fusible compounds, while among these oxides some are not
fusible per se. Chloride of lead, heated with iron filings, and with or without sulphur
orms an excellent alloy which yields spongy lead. No difficulty is experienced with
the following alloys: Chloride of lead with Chloride of copper separates in forms of
long crystals, and can be converted into the oxide by milk of lime, such crystalline
chlorine of lead treated with metallic zinc in a slightly acid solution will give pure
metallic lead.
This combination of lead with metals and other materials cast in a mould, allows me
to manufacture plates of any size, or shape, or rods, sticks, cylinders and blocks of
concreture, hard puce peroxide of lead, and of spongy pure metallic lead.

page_text: I use common moulds and crucibles, but when large quantities of large plates
must be cast, I may employ a melting pan. Sometimes, I make perforated plates or
blocks, so that the formation may be more rapid, and my plates being naturally strong
and hard, are not modified or disingrated in their structure by these holes which
render the penetration of the current more intimate and more rapid. I must note that
sometimes, I use platinum to increase the rate of discharge and that in certain
circumstances, I platinize my porous lead.
I do not confine myself to an electrolyte of diluted sulphuric acid, but may
employ, according to the nature of my alloys a solution of acid mixed with other
substances.
The plates or rods I manufacture, according to the above description, can be
adopted for secondary as well as for primary batteries, but in the latter case, porous
lead may be replaced by a suitable electrode, which will not be made of porous
lead.

page_text: EMILE ANDREOLI, journalist 62 Loughborough Park Brixton, Surrey do hereby
declare the nature of my invention for PLATES WITHOUT SUPPORT ENTIRELY MADE OF
ACTIVE MATERIAL, FOR VOLTAIC BATTERIES and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement:
The nature of this invention consists in the application of metallurgical, chemical
and electrical methods for constructing dense crystalline, homogeneous conductive and
cohesive plates to be used as the positive or anode and as negative or cathode in
secondary batteries.
of
Each of these electrodes which are made of pure active material without any
oxidisable or non oxidisable support or in case I desire to increase the conductivity
the plates, with an internal skeleton of thin wire or its equivalent, provided it is not a
support or retainer, are entirely composed, on one side of pure porous lead or other
porous metal, and on the other side, of pure peroxide of lead or of other metal, and it
has internally and externally a very large surface which allows me to produce a highly
efficient battery.
This improved system for the manufacture of electrodes, is based upon the principle
of utilizing metallic salts in combination by fusion with other metallic salts, substances
or compounds and especially for utilizing fused salts of lead combined with other
metallic or non-metallic salts and submitted to a treatment of purification and of
electrolytic formation and according to the requirements and qualities I desire to
impart to the plates, i.e. to the use the battery is intended for, I may alter or modify
the respective proportions of the compounds of my electrodes, in order for instance,
to raise or to lessen the point of fusion, and obtain a greater or smaller degree of
porosity, and consequently to change the density of the material.
In carrying out this invention, I mix, fuse and cast in appropriate moulds metallic
salts and substances, and by a special treatment, which I shall hereinafter describe, I
transform these castings of any size or shape, which in course of this specification,
I will call the "Plates," and which were inert, into electrodes made of pure active
material, free from any extraneous matter, which are able to store electric energy and
are not liable to become disintegrated by the continuous charging and discharging in
their normal use.

page_text: If the salts and substances I fuse and cast, and which, after, I decompose and
convert by heat, chemical affinity or dissociation or otherwise into pure spongy reguline
lead or other metal, and if the process itself of "reducing" those fused substances or
compounds and alloys are such as are known and used by metallurgists and chemists,
I nevertheless insist upon this point as being the characteristic feature of this invention,
that I combine by fusion in certain proportions some metallic, alkaline or earthy
materials and more particularly metallic chlorides, chloride of lead and salts of lead
which once purified and converted into reguline metal are electrolytically "formed,"
when their nature appearance, etc., have been allotropically and otherwise modified,
improved and transformed, viz. when such plates have been brought to the state of
pure active substance, without the aid of any mechanical pressure whatever, which
would destroy the regularity of the honeycombed cells of the crystalline metal, the
cohesion of the molecules, their porosity and conductivity as well as it would affect
their capacity for absorbing gases.
Although for reasons of cheapness, I use in preference lead salts, I do not confine
myself to this metal alone, its chloride, sulphate, phosphate, etc., in combination one
with the other, or in admixture with zinc or chloride of zinc or with other chlorides
or substances, but having found that several metals, their chlorides and other salts,
either alone or in combination one with the other or with other substances, particularly
with chloride of lead and salts of lead, can be successfully utilized I include in this
method, the employment of metallic compounds and particularly of salts fused with
chlorides, such as chloride of lead, and which having been submitted to a process of
purifying and refining are turned into an anode and a cathode entirely made of
absolutely pure material, and which, once polarised are capable of yielding a powerful
secondary current.
The production of my plates is neither complicated nor expensive and does not
require any skilled labour; they are firm in their structure they are self sustaining,
they do not disentegrate or break, and they contain more active substance than the
plates constructed by other systems.
There are several combinations for blending, melting and fusing metallic salts,
sulphates, chlorides and other salts of lead and of other metals; but while applying
the igneous principle, i.c.: the fusion of substances mixed together and which
transform into positive and negative electrodes for secondary batteries, I will merely
refer in this description to the process for treating fused lead salts such as in preference:
Chloride of lead, in admixture with sulphate of lead or other salts of lead, or of other
metals with or without addition of caustic potash or soda, or carbonate of soda or
potash, or of fluor spar, or of iron filings or copper filings, or with a paste of peroxide
of manganese, in hydrochloric acid, or with zinc or chloride of zinc, etc.
Chloride of lead fused with sulphate of lead gives very satisfactory results, with
and without addition of a small quantity of solid or liquid chloride of zinc. Chloride
of lead fused with sal-ammonia answers admirably any purposes.
Phosphate of lead combines readily with Chloride of lead, as well as Litharge does
when heated with various substances some of which are not fusible per se, it forms
fusible compounds; but for some purposes, I find it advantageous to melt Chloride
of lead and a very small quantity of Chloride of zinc, with a paste of peroxide of
manganese and hydrochloric acid which forms an excellent alloy and yields a splendidly
crystalline mass of spongy metal. I also sometimes fuse chloride of lead with chloride
of sodium, but then the crystals I obtain are not so perfect; many are the examples
I can give of the metallic salts and compounds which can be fused, reduced and
peroxidised and which I have experimented, but I will add only one more illustration
of the combined substances I form by their fusion with Chloride of lead and will
recommend the use sulphate of zinc with chloride of lead, which satisfies me almost
as much as the paste of peroxide of manganese with chloride of lead hereinabove
described.
When cast, the plates have their edges trimmed on an emery wheel, so that they
might be framed without difficulty and both their faces are smoothed with glass paper
or otherwise.

page_text: Chloride of lead melts below redness, but great care must be taken not to heat the
mixture too much as an evolution of copious fumes would ensue and a great loss
would be caused by the volatilization of chloride of lead and zinc. When this process
will be worked on a large scale and quantities of plates will be cast, I will employ a
melting pan so constructed that the heat being uniform and the fusing point never
exceeded, the fusion will be perfect and there will not be any loss.
I generally make massive plates, but when it occurs that I want to increase the
conductivity of the peroxide electrode, i.e., obtain a higher rate of discharge, I imbed
in it, not a grid or supporter, but a light skeleton of thin platinum wire, or of a fine
thread of lead which I have previously peroxidised or coated with a film to prevent it
from melting when in contact with chloride of lead which has a higher point of fusion
than lead. A good conductor is made of a very thin and light lead piping, in which a
core of extremely fine copper is inserted, which has a great conductivity and is
protected by the lead sheath against the action of electrolysis. I also frequently cast
plates with many rather large holes, in order to have these perforated plates more
rapidly formed and to render them apt to give a higher rate of discharge, while,
being at the same time porous but firm, they are not in the least disintegrated or
modified in their shape and structure or destroyed by these holes which render the
penetration of the current more intimate. In certain cases, when a higher rate of
discharge is required, I pass through these holes, a very thin thread of platinum or
other non oxidisable or little oxidisable metal or of copper coated with or imbeded in
a lead piping as above defined, and thereby I multiply the contacts in the anode by
this intertwining of metallic thread which is stitched through the holes and forms a
reticle with contacts, not only on the two faces of the plates, but along their internal
section. The plates are generally very hygrometric and when I do not at once frame
them before being submitted to treatment, they are kept in a damp place and thus the
chloride of zinc or other chloride percolates and sweats.
They are carefully wiped, dried and warmed in a mould where molten lead or a
molten alloy of lead and tin or antimony, or any suitable alloy is cast round their
edges in shape of a light frame with terminals for connecting the plates.
The plates are converted into porous lead by zinc, Iron or other reducing agents,
or by the combined action of Iron and zinc in a hot or cold solution of Sal Ammonia
or of Chloride of Magnesium, or of Staffurt salts and preferably of Carnallite. There
are several Chlorides which form a suitable solution, but Chloride of Zinc, in my
experience to the present, gives the best results.
If I treat electrolytically the castings in order to eliminate Chlorine, the electrolyte
may be a solution of Sulphuric Acid or of Sulphate of Ammonia, or of Sal Ammonia
or of Alkalies, such as Caustic Potash or of Sulphuric Acid with a certain proportion
of Peroxide of Manganese to prevent the noxious fumes of Chlorine and to peroxidise
rapidly I may also employ a solution of Hydrochloric Acid. This mode of converting
Chloride of lead and salts of lead fused either alone or separately or one with the
others or with other metallic salts is a well known process in chemical and electrical
laboratories and also in metallurgy and chiefly in the desilverization of lead ores, but
I do not believe, within my knowledge that such compounds have ever been made of
chloride of lead and other salts of lead combined as above recited with different
substances such as chromic acid, peroxide of manganese, permanganate of potash, etc.
and reduced in appropriate solutions such as chloride of zinc or of magnesium or of
carnallite etc., with a view to have a better crystallisation, and besides, whether I
render the metallic salt porous by electrolysis or by reducing agents which allotropically
modify the molecular structure of the plates, my main object is to remove entirely
Chlorine without evolution of noxious smell and of dangerous fumes without loss of
time and at cheap rate.
Chloride of lead fused with sulphate of lead and zinc or chloride of zinc or with
other salts of lead or other metals with addition of zinc or its chloride is quickly
reduced in a cold solution of ammoniacal salts, but its metallization is far more effective
and rapid in a bath of chloride of zinc at a moderate temperature.
As soon as the reduction has taken place, I immerse the plates in boiling water

page_text: and I wash them thoroughly several times, then I neutralize chlorine in a hot bath of
water and alkalies, carbonate of potash or soda, etc. and the solution is kept hot a
little time. The plates are afterwards plunged in a solution of sea salt (but this is not
necessary and I can dispense with it) and finally washed in boiling water.
On a large scale, these washings will be performed without difficulty, trouble and
waste of time by the use of steam and also of taps to let run and replace the liquids
from which for instance, the zinc or chloride of zinc or other substances or even the
salt may be recovered and utilized by some known process.
The advantages of reducing the cast plates by electrolysis are undeniable, but in my
opinion their reduction by zinc and Chloride of zinc or of ammonium or of magnesium
is more regular and rapid and therefore is preferable. The consumption of zinc may
seem rather considerable, but this expense after all is a very small item, as not only
the zinc can be recovered, but the solutions may give by-products such as zinc oxide
or Chloride of calcium, Sal ammonia artificial Calamine, etc.
Assuming that 20 or 25 per cent. of zinc per ton of plates are necessary for the
reduction by zinc would still bear favourably comparison with the cost of reduction by
electric current which requires a great number of Ampere hours to bring Chloride of
lead to the porous state and to purify it from all traces of Chlorine. I must add that
the reduction by zinc or iron presents this great advantage that it saves trouble,
attendance and that there are no accidents which may possiby happen as it is the case
when the plates are reduced by a current from a dynamo.
In carrying out this dissociation of Chloride of lead, etc., I place in a tank my plates,
and between every two of them, there is a sheet of zinc. The solution is distilled or
rain water with a small quantity of Chloride of zinc or of ammoniacal salts, etc.; heat
may be applied and when the above described operation of metallization has taken
place, my plates present internally and externally the appearance of a brilliant spongy
but very soft lead which I harden and make more cohesive in a solution of sulphuric
acid and water.
In the production of my plates I find convenient to use Chlorides and more
particularly Chloride of lead fused with other substances because Chlorine in
combination with salts of lead and other metals has a tendency to cristallize them and
is a powerful agent of metallization.
I am well aware that several attempts have been made and even that patents have
been taken with a view to secure the exclusive right of employing in the manufacture
of electrodes for secondary batteries, salts of lead and especially Chloride of lead
"fused and reduced to the metallic state by electrolysis and the construction of a
battery by reoxidation of one of the poles," but many years ago, Marci Davy had already
employed in his batteries Chloride of lead and also Chloride of silver which he reduced
to the metallic state by means of zinc and water. The reduction of chloride of lead
is therefore common property, and so is also the reduction of fused Chloride of lead
by electrolysis which was experimented and demonstrated by Faraday.
It may be that some chemists, electricians metallurgists and specialists in the art of
treating lead ores had thought they had a right of patenting as a new departure and
original idea and novel invention the very well known properties of chloride of lead
and also of several "insoluble or only slightly soluble salts of lead" for fusing and
being reduced by zinc or electrolysis. But it is not sufficient to cast a plate, and
by an old process used in metallurgy, to render it porous, because that plate, in its
impure state, will neither be a good anode, nor a good cathode, and unless treated and
thoroughly cleaned and refined, is quite worthless. There a very few persons who
know what Chloride of lead really is, alone or in combination with other salts, and
what can be done with it, more especially in Electricity. In the treatises of Chemistry,
there are but a few lines on this Haloid salt, and most of these books repeat the same
scanty information or the same errors; very often, there is no mention of it in the
tables of the metallic chlorides, and in modern books, like Miller's Chemistry and
others, it will be found that Chloride of lead, when fused is a horny "sectile "mass,
which can be cut with a knife, while on the contrary it is very difficult to cast it alone,
because it expands, and being very brittle, breaks by contraction and falls to pieces,

page_text: and finally cannot be cut at all. Unless the operation is performed in a certain
manner, there is almost an impossibility to construct plates made of Chloride of lead
fused and cast alone; and it is still more impracticable to use them as electrodes
because they do not resist manipulation and would infallibly break. But, even
assuming that they do not break and have been converted into porous lead, they never
will work as electrodes in a secondary battery unless they have been subjected to a
treatment with the object of eliminating Chlorine, which, after it has rendered such
valuable services as an agent of crystallization and metallization of Chloride of lead,
has become a dangerous enemy, because as long as the pores of the spongy mass, are
contaminated by the presence of chlorine, there is no possibility for producing a pure 1
plate of spongy or peroxidised lead, and the plates will buckle and disintegrato,
oxychlorides will be formed and there will be a strong evolution of unpleasant smell
and of noxious gases. It would therefore be an idle and futile pretension to claim as
a novel and original invention in the manufacture of electrodes for accumulators, the
fusion and reduction of Chloride of lead; the problem of the transformation of Chloride
of lead into pure spongy and pure peroxidised lead is far more complicated and has
never been solved up to this day, except by this system for treating Chloride and
other salts, of which I am now giving the description.
My plates may be considered as free from Chlorine after their repeated washings
and the consecutive baths they have been subjected to; but I do not content myself s
with this mode of dechlorination, however powerful and efficient it may be, and I
complete it by passing a current from a dynamo, during a short time, in an electrolytic
tank where each plate acts as a negative electrode and is placed opposite a sheet of
lead which acts as a positive electrode and on which Chlorine goes, and all the
The sheets of lead become
impurities, extraneous matters and salts are transported.
soon peroxidised and the film of peroxide which coats them can be scraped and
washed and then utilised in the construction of primary batteries. Sometimes, in this
eliminating Chlorine, my electrolyte is a solution of Hydrochloric acid, and in such
case, the anodes turn whitish or yellow; the liquid too, under the action of the current
becomes yellow, and I ascertain that the elimination of Chlorine is at an end when
the electrolyte is as clear as water, and hydrogen is evolved instead of Chlorine.
During this operation, as well as when I peroxidise or recharge the plates, I use as
separators, 1. 2 or 3 pieces of coarse canvas (according to the requirements) of the
same size as the plates, and which have been previously boiled in paraffin, in such a
manner that the tissue forms an insulating separator while its interstices remain open
and give free access to the gases. These separators may also be made of an asbestos
network or of a horsehair gauze which has been coated with an insulating substance.
The plates having been withdrawn from the electrolytic tank, are dried or rather
roasted so that they oxidise, and their pores being condensed, they are strong and can
be manipulated without any risk of breaking. If struck with a piece of glass, wood
or of metal they render a metallic sound, and they internally present a fracture of pure,
crystalline, reguline lead. There are several manners for drying the plates; I may
place them in an oven, where there is a draught and the air circulates, or place
them on a wire netting at about one inch over a sheet of iron resting on a gentle fire,
so that, not only the moisture evaporates and the plates are firm and hard, but the
pure lead is converted into a suboxide and therefore more rapidly peroxidised, because
the peroxidation of oxidised lead requires less ampere hours than pure spongy lead.
The plates are now ready for peroxidation and 1 charge them in a suitable electrolyte
such as sulphuric acid and water, or sulphuric acid and water with addition of
a manganese salt or of peroxide of manganese when peroxide of lead has commenced
browning the anodes. I never reverse the current, and I may use in charging a
higher intensity than it is generally the case with other accumulators.
Having now particularly described and ascertained the nature of my said invention
and in what manner the same may be performed, I declare that what I claim is:
1. The application of iny improved method of constructing electrodes for secondary
batteries in any size or shape, with or without internal conductors of non oxidizable

page_text: lor of thin peroxidised lead piping or wire having inside a core of very fine silver
opper thread, but without any oxidisable or non oxidisable support or retainer
tever, such electrodes being entirely made of self standing pure active material.
The production of electrodes entirely made of active and pure material by a
od of fusing and casting salts of lead or of other metals, in combination with
r salts of lead or other metals, or with alkaline or earthy substances etc., but more
icularly of using metallic chlorides and namely chloride of lead combined with
hate of lead and other salts of lead or other metals, or with sulphate of zinc or
a salt of manganese or of copper, or with peroxide of manganese or with caustic
sh, or with Chromic acid or permanganate of potash, or with Chloride of
onium or Calcium or with fluor spar and other substances as herein before recited
particularized or with their equivalent.
The choice of the different salts or substances I fuse with Chloride of lead and
of the different solutions, I use for the reduction baths, in order to obtain a better
ing and a perfect crystallization substantially as above set forth.
The cycle of operations herein described as the whole of my system, viz.:
a. The treating and refining metallic salts especially salts of lead and more
particularly Chloride of lead fused and cast in combination with different
substances, compounds etc., of which I gave a list in this specification or their
equivalent.
b. The method of purifying such combined salts and in particular Chloride of
lead and of partially removing Chlorine from plates (which have been
reduced and allotropically transformed into impure spongy lead,) by
ammoniacal solutions as hereinabove specified, and by immersion of the plates
in alkaline, sea salt and boiling water to neutralize Chlorine and eliminate it
as well as zinc.
c. The employment of electrolysis by passing a current from a dynamo or
any other convenient source of electricity as hereinbefore specified until there
is not the slightest trace of Chlorine in the plates to be used as electrodes in a
secondary battery, after they have been dried and roasted and charged and
"formed" in a suitable electrolyte by the current from a dynamo.
d. The employment as an electrolyte in the electrolytic tank for eliminating
Chlorine of Alkalies or of hydrochloric acid or of Sulphuric acid and water,
with addition of peroxide of manganese in order to obtain a pure reguline,
crystalline lead easy to peroxidise.
e. The arrangement in the completion of the dechlorination in the electrolytic
tank of the plates, which all act as cathodes in presence of or between sheets of
lead which all act as anodes in the manner and with the object substantially as
above set forth.
f. The admixture of a manganese salt in the electrolyte of sulphuric acid and water
when the positive plates commence to peroxidise and especially of peroxide
of manganese substantially and for the purposes hereinbefore described.
JL: CL CM 1007