IMPROVEMENTS IN THE MEANS OF AND IN THE APPARATUS FOR STORING ELECTRICAL ENERGY AND IN THE PREPARATION OF THE MATERIALS TO BE EMPLOYED " PROVISIONAL SPECIFICATION
Year: 1882

page_text: LETTERS PATENT to John Evelyn Liardet of Brockley in the County of Kent
and Thomas Donnithorne of Gracechurch Street in the City of London for
an Invention of "IMPROVEMENTS IN THE MEANS OF AND IN THE APPARATUS
FOR STORING ELECTRICAL ENERGY AND IN THE
PREPARATION OF THE
MATERIALS TO BE EMPLOYED "
PROVISIONAL SPECIFICATION left by the said John Evelyn Liardet
& Thomas Donnithorne at the Office of the Commissioners of Patents on
the 9th January 1882.
JOHN EVELYN LIARDET of Brockley in the County of Kent and THOMAS
DONNITHORNE of Gracechurch Street in the City of London "IMPROVEMENTS IN
THE MEANS OF AND IN THE APPARATUS FOR STORING ELECTRICAL ENERGY AND
IN THE PREPARATION OF THE MATERIALS TO BE EMPLOYED "
This Invention has for its object improvements in the means of and in the
apparatus for storing electrical energy and in the preparation of the materials to
be employed.
1. The secondary batteries of M. Planté and M. Faure & M. De Méritens are
all worked upon the same principle which may be briefly stated as follows.
Acidulated water is decomposed by means of an electric current into hydrogen and
oxygen gases with the view of utilizing the oxygen gas on the one hand to assist
in the formation of peroxide of lead at the positive pole (originally consisting of
lead in whole or in part) and of subsequently utilizing the hydrogen gas which
condenses upon the kathode to reduce the peroxide of lead to a lower state of
oxidation or even to a metallic condition the negative pole (consisting of lead
wholly or in part) being at the same time converted partly into oxide of lead.
2. To further illustrate the principle stated above when water acidulated with
dilute sulphuric acid is electrolysed using plates of lead as electrodes the plate at
which the current enters becomes coated in course of the decomposition with brown
peroxide of lead and this substance being powerfully electro negative towards the
metallic lead and the film of hydrogen at the kathode plate, the cell is now capable
Price 8d1

page_text: 4
of producing an electric current if and after it is detached from the battery by
means of which it was originally or primarily charged. By discharging such a
'formed" cell the peroxide of lead is in part reduced to a spongy or loosely
crystalline metallic state and if now the cell be again charged from a primary
battery or other source of electric current in the opposite direction the other plate
of lead becomes peroxidised and the hydrogen gas in being liberated less freely.
than upon the first charging because it reacts upon the peroxide of lead and
reduces it to the metallic slate. By thus charging and recharging a number of
times there is ultimately obtained relatively great amounts of peroxide of lend
upon the one hand and finely divided or spongy metal upon the other hand.
3. The quantity of potential energy thus admitting of storage so to express it,
depends entirely upon the amount of electro-chemical work done and this in its
turn is directly proportional to the extent of surface of the plates, other conditions
being constant.
4. Knowing the nature of the work which is performed in forming such accumu-
lators that is to say knowing the substances which result as products of the action
it is a step towards simplification if instead of starting with metallic lead alone,
there is used in addition thereto a quantity of the peroxide of lead or any other
oxide of lead intermediate between lead and its peroxide. Similarly since the
greater the surface of the plates the greater is the action, it is of advantage to start
with the plates so constructed as to present the greatest possible surface.
5 Many attempts have been made towards accomplishing these desirabilities
and our Invention relates in part to the same subjects.
6 It is not essential however to the so called storage of electric energy that lead
plates should be used for the electrolysis of water; other metals and substances
may be employed and other products consequently result from the action, but in
all cases it is sought to obtain as relative products two or more substances which
present differences in the amount of their potential energy so that in their
neutralisation or running down to the same inert level, force in the form of an
electric current is developed and our Invention relates in part to this subject.
7 In those cases where we employ metallic lead we employ it in the shape-
A of cells of any shape packed full with lead shots. B. of cells of any shape
packed full with hollow spheres of lead prepared as follows We mould or other-
wise prepare marbles or round balls or squares or other forms of chalk or other
substances which are known to be soluble in or dissolved by water or acids, or
alkalies or other solvents and then coat them with a film of lead by rolling them
about in molten lead or otherwise after which they are removed from the bath of
lead, suitably pierced so as to break the coating of metallic lead in one or more
places and then immersed in the solvent or reagent which exercises the solvent or
decomposing influence capable of removing the matter which forms the contents of
the leaden spheres or shells. For instance we employ chalk which is decomposed
by hydrochloric acid or common salt which is soluble in water. C of cells of any
shape packed with broken charcoal, coke asbestos, pumice stone, sand or other
material presenting an extended surface which has been previously coated with
metallic lead either as described in (B) or by electrolysing acetate of lead solution
in which such porous substances are immersed or D we employ lead in that
particular tree like form or spongy crystalline condition in which it is deposited
from a solution of acetate of lead when metallic zinc is placed in such a solution.
Such spongy lead may be packed in cells or leaden vessels of any shape and size to
serve in the place of plates in the secondary batteries or accumulators or it may
be attached to any leaden or other metallic surface of any nature or description.
Or plates covered with the spongy metal may be used after being prepared as
follows. Plates of lead are taken and to each surface is attached by means of
leaden rivets or otherwise a sheet or plate of metallic zinc
Such prepared
compound plates are then suspended in solution of acetate of lead until the zinc is
dissolved out into the solution and substituted by lead in the spongy condition
already described.

page_text: 8 All such forms of lead as are described in (7) may be coated if desired with
any oxide of lead or the sulphate of lead.
9 In the place of a coating or paint of per oxide of lead or red lead or other
suitable lead compound to be attached to the plates of lead, we employ more or
less thick cakes of such substances prepared in the first place by suitable chemical
means and then compressed in blocks or moulds and attached to the metallic
plates by means of leaden rivets or hooks or by bandages or strips of gutta percha
or felt or other suitable material. Similarly other cakes may be employed such
for instance as we obtain by mixing any proportions of red oxide of lead or
peroxide of lead or sulphate of lead with plaster of Paris or other like cement and
water with or without the addition of other inert substances presenting an
extended surface such as powdered glass pumice charcoal asbestos gypsum &c. &c.
10 We also uso tin plates in the placo of lead plates and other forms of the
metal tin in the place of corresponding forms of the metal lead as herein before
described, covering the surfaces where desirable with a paint or coating or cake or
deposit of any oxide of tin, and in particular the dioxide of tin. In the case of tin
we also employ granulations of the metal for packing in cells to be used as electrodes
and for attaching by any gum or glue or other substance to the surface of tin
plates or corrugated sheets &c.
11 In further relation to the use of spongy lead more particularly described
in (7 D) we can also attain our object by filling a cell with acetate of lead solution
immersing as electrodes two plates or other forms of zinc and then so soon as the
zinc is dissolved and replaced by metallic lead drawing off the solution, washing
out the cell if necessary and refilling it with dilute sulphuric acid and proceeding
"to charge or form" the cell as if we had started with plates of lead Or instead
of starting with both electrode like plates of zinc alone, we can start having one
composed of zinc and the other of lead encased in a coating or cakes of any of the
compositions described under (9) Or again we can start with one free plate of
zinc and the other plate enclosed in such a coating or cakes as described under (9)
or such cakes or coating in which compounds of tin have been used in the place of
compounds of lead.
We provide the battery cells with air tight covers and make suitable provision
by valves for the escape of gas should any be liberated.
In those cases in which the battery cells are started with surfaces of metallic
lead we add peroxide of hydrogen to the dilute neid in which they are immersed.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said John Evelyn Liardet & Thomas Donnithorne in the Great Seal
Patent Office on the 7th July 1882.
"
JOHN EVELYN LIARDET of Brockley in the County of Kent and THOMAS
DONNITHORNE of Gracechurch Street in the City of London IMPROVEMENTS IN
THE MEANS OF AND IN THE APPARATUS FOR STORING ELECTRICAL ENERGY AND
IN THE PREPARATION OF THE MATERIALS TO BE EMPLOYED'
"
This Invention has for its object improvements in the means of and in the
apparatus for rendering energy potential or so to speak of storing it and in the
preparation of the materials to be employed therein.
1. The secondary batteries of M. Planté and M. Faure and M. De Méritens are all
worked upon the same principle which may be briefly stated as follows.
Acidulated water is decomposed by means of an electric current into hydrogen and
oxygen gases with the view of utilising the oxygen gas on the one hand to assist
in the formation of peroxide of lead at the positive pole (originally consisting of
lead in whole or in part) and of utilising the hydrogen gas which condenses upon
or is liberated at the negative pole to reduce the peroxide or other salt of lead to a
lower state of oxidation or even to a metallic condition.
2. To further illustrate the principle stated above when water acidulated with
dilute sulphuric acid is electrolysed using plates of lead as electrodes the plate at
which the current enters becomes coated in course of the decomposition with brown
peroxide of lead and this substance being powerfully electro negative towards the
imetallic lend and the hydrogen which is liberated at the negative plate, the cell is
now capable of producing an electric current if and after it is detached from the
battery by means of which it was originally or primarily charged. By discharging
such a "
formed cell the peroxide of lead is reduced and if now the cell be again
charged from a primary battery or other source of electric current in the opposite
direction the other plate of lead becomes peroxidised and the hydrogen gas is now
liberated less freely than upon the first charging because it reacts upon the oxide
of lead and reduces it to the metallic state. By thus charging and recharging a
number of times there are ultimately obtained relatively great amounts of peroxido
of lead upon the one hand and finely divided and crystalline metal upon the other
hand.
"
3 The quantity of potential energy thus admitting of storage so to express it
depends entirely upon the amount of electro chemical work done and this in its
turn is proportioned to the extent of surface of the electrodes other conditions
being constant.
+ Knowing the nature of the work which is performed in "forming" such
accumulators that is to say, knowing the substances which result as products of
the action it may be a step towards simplification if instead of starting with
metallic lead alone, there is used in addition thereto a quantity of the peroxide of
lead or any other oxide of lead intermediate between lead and its peroxide or other
suitable salt of lead such as the sulphate of that metal. Similarly since the greater
the surface of the electrodes the greater is the action it is of advantage to start
with the plates or electrodes so constructed as to present the greatest possible
surface.
5 Many attempts have been made towards accomplishing these objects and our
Invention relates in part to the same subject.
G It is not essential however, to the so called electric storage of energy that
lead plates should be used for the electrolysis of water other metals and substances
may be employed and other products consequently result from the action but in

page_text: all cases it is sort to obtain as relative products two or more substances which
present differences in the amount of their potential energy so that in their
neutralisation or running down by chemical reaction to the same inert level, force
in the form of an electric current is developed and our Invention relates in part to
this subject.
7 In those cases where we employ metallic lead we employ it in the shape
A Of cells or structures of any shape packed or filled with lead shots.
B. Of cells or structures of any shape packed or filled with hollow spheres of
lead prepared as follows we mould or otherwise prepare marbles or round balls
or squares or other forms of chalk or other substances which are known to be
soluble in or dissolved by water or acids or alkalies or other solvents and we then
coat them with a film of lead by rolling them about in molten lead or otherwise,
after which they are removed from the bath of lead suitably pierced so as to break
the coating of metallic lead in one or more places and they are then immersed in
the solvent or reagent which exercises the solvent or decomposing influence
capable of removing the matter which forms the contents or cores of the leaden
spheres or shells.
For instance we employ chalk which is decomposed by hydrochloric acid or
common salt which is soluble in water.
C Of cells of any shape packed with broken charcoal, coke, asbestos pumice
stone sand or other material presenting an extended surface which has been
previously coated with metallic lead either as described in (B) or by electrolysing
à solution of the acetate or other soluble salt of lead in which such porous
substances are immersed. Or
1 We employ lead in that particular porous and finely divided condition in
which it is deposited from a solution of acetate or other salt of lead when metallic
zinc is placed in such a solution. Such finely divided and porous lead may be
packed in cells or leaden or other suitable vessels or on supports of any shape and
size to serve in the place of plates in the secondary batteries or accumulators or it
may be attached to any leadon or other metallic surface of any suitable nature or
description. Or plates covered with such porous metal may be used being prepared
as follows-Plates of lead are taken and to each surface is attached by means of
leaden fastenings or otherwise a sheet or plate of inetallic zinc. Such prepared
compound plates are then encased in a suitable jacket of porous material such as
felt or sacking and then suspended in a solution of acctate of lead or other salt of
lead until the zine is dissolved out into the solution and substituted by lead in the
finely divided and porous condition already described.
8 All such forms of lead as are described in (7) may be coated if desired with
any oxide of lead or the sulphate of lead.
In the place of a coating or paint of peroxide of lead or red lead or other
suitable lead compound to be attached to the plates of lead or other forms of that
metal herein before referred to we employ more or less thick cakes of such
substances prepared in the first place by suitable chemical means and then com-
pressed in blocks or moulds and attached to the metallic plates by means of leaden
fastenings or hooks or by bandages or strips of gutta percha or felt or other
suitable material. Similarly other cakes may be employed such for instance as wo
obtain by mixing any proportions of red oxide of lead, or peroxide of lead or
sulphate of lead with plaster of Paris or other like cement or with china clay or
other similar earths and water with or without the addition of other inert substances
presenting an extended surface such as powdered glass pumice charcoal asbestos
gypsum &c. &c. and such cakes may be surrounded by a further casing of pure
plaster of Paris with the view of preventing the formation in the solution of the
battery of a deposit of metal liable to impair the usefulness of such battery.
In our Provisional Specification we included the use of tin plates and other
forms of the metal tin but further experiment has shewn us that tin is not as
suitable for our purpose as we at first thought it would be and we therefore do not
include tin amongst the metals we propose to make use of.

page_text: 10 In further relation to the use of the finely divided porous lead more
particularly described in (70) we can also attain our object by filling a cell having
two compartments with a porous wall between them with acetate of lead solution
immersing as electrodes two plates or other forms of zinc encased in suitable jackets
one in each compartment and then so soon as the zine is dissolved and replaced by
metallic lead, drawing off the solution washing out the cell if necessary and
refilling it with dilute sulphuric acid and proceeding after providing the cell with
suitable terminals to charge or "form" the cell as if we had started with plates of
lead. Or instead of starting with both electrode like plates of zinc alone, we can
start having one composed of zinc and the other of lead encased in a coating or
cakes of any of the compositions above mentioned in paragraph 9 Or again we
can start with one free plate of zinc and the other plate enclosed in such a coating
or cakes as above mentioned in paragraph 9.
We may provide the battery cells with air tight covers and make suitable
provision by valves for the escape of gas should any be liberated.
In those cases in which the battery cells are started with surfaces of metallic
lead we can add peroxides of hydrogen to the dilute acid in which they are
immersed in order to assist in the formation of peroxide of lead.
11 And in order that our Invention may be fully understood we shall now
proceed to describe more particularly the same and for that purpose shall refer to
the several Figures on the annexed Sheet of Drawings.
Figure 1 of the accompanying Drawings represents a vertical section of a battery
constructed according to this Invention as herein after described.
Figure 2 is a vertical section of another form of a battery constructed according
to this Invention as hereinafter described.
Figure 3 is a vertical section of another form of battery constructed according to
this Invention as hereinafter described.
Figure 4 is a vertical section of yet another form of battery constructed
according to this Invention as herein after described.
According to the arrangement illustrated in Figure 1 a pair of terminals A and B
having flat and parallel surfaces is employed the said terminals being composed of
two thin plates of lead or carbon and each surrounded by a coating of the finely
divided porous lead D herein described and this porous metal in its turn being
surrounded by a coating or composition of red lead peroxide of lead sulphate of lead
or other suitable lead compound and plaster of Paris, or the other materials above
mentioned. E in the proportion for example of 8 parts of the lead compound and
1 part of plaster of Paris or the other materials above mentioned the whole being
placed in a rectangular vessel Ceontaining water acidulated with sulphuric acid.
Figure 2 illustrates a battery provided with two terminals of carbon or lead or
other conductor A and B embedded in and therefore in contact with a mass of lead
shots or porous lead D packed in eells E of the same metal or composed of some
porous material and the whole contained in suitable vessel C filled with acidulated
water Or the lead shots or porous lead as the case may be, may be first mixed
with red lead either in one or in both cells.
Figure 3 represents a battery constructed similarly to that illustrated in Figure 2
except that the containing cells of lead E are pierced with holes and encased in a
coating F of red lead or other compound of lead mixed with plaster of Paris or
other composition as above mentioned.
Figure 4 illustrates a battery having one terminal made of metallic lead sheet
A surrounded by and encased in a mass of finely divided porous lead D which in
its turn is kept in its place by thin folds of lead foil (but in place of the lead foil a
coating of plaster of Paris or the other materials above mentioned may be employed)
the other terminal B being composed of carbon surrounded by and encased in a
coating or casting E of the before mentioned mixture of red lead or other compound
of lead and plaster of Paris or other materials.
In the case of the Faure and Sellon, Volckmar, batteries sheets or plates or other
forms of lead are employed the lead however always presenting more or less plain

page_text: "
or continuous surfaces and comparatively great massiveness or solidity while in
red lead or other compound used instead thereof is either kept in contact with the
said sheets or plates by means of flannel felting or parchment or other destructible
material or else is deposited in holes crevices or cavities made by mechanical means
in the lead sheets or plates. In such cases it is only after the batteries have been
in use for some considerable time that there is obtained-(and it is so obtained by
the "formation as it is termed of the batteries) any appreciable amount of
crystalline lead which in such case results from the process of reduction of a lead
compound say of the red oxide by hydrogen and until that point is reached the
cells are not thoroughly receptive in character. On the other hand our batteries
constructed as described particularly as illustrated by Figure 1 are perfectly
receptive from the beginning and before they are actually employed for we start
with lead the whole of which is already in an exceedingly porous state thus pre-
senting a most extended surface very active and being relatively light as compared
to sheets plates or even wire or foil. Our lead is therefore in the condition of
being most susceptible to the influence of oxygen which it absorbs with great
avidity thus giving to our batteries exceptional receptivity of character. Not only
this but by mixing plaster of Paris or the other materials above mentioned with
the red lead or other compound of lead to be used in conjunction with the porous
metal we are enabled to place the said lead compound just as and where it is
wanted without the aid of any further support and the plaster of Paris and
materials above mentioned being of a porous nature give to the red lead or other
compound a like character and bestow on the whole cell the valuable property of
comparative indestructibility. In this form of battery (Figure 1) therefore which
we prefer the poles or terminals which may be made of carbon or any other suitable
material are simply intended to serve as conductors for the flow of the electric
currents into and out from the cells themselves. In this respect, that is to say, the
use of porous lead only on the one hand and the use of a lead compound mixed
with a porous cement on the other hand, our process and apparatus are quite novel
and most important. We may of course also use the plaster of Paris or such of the
materials above mentioned as are suitable for the purpose as a cement for binding
whole series of cells together and we can arrange or connect up the members of the
said series in the ways that are well known in order to obtain quantity and tension
effects.
As regards the preparation of the porous lead which we employ we prepare it
by the following processes or modifications direct from the ores of lead such as
galena or native sulphide of lead as follows.-According to our process the ores are
crushed and decomposed by means of any suitable acid such as hydrochloric acid
in a closed mill or other suitable apparatus the hydrochloric acid if employed con-
verts the lead into chloride of lead which after being washed with common water
(chalk being used for the neutralization of any excess of acid) may be extracted
by means of boiling water from the clear solutions which result from this pro-
ceeding the porous lead is precipitated by means of scrap zine or other forms of
spelter immersed or suspended in the said solutions and the sulphurated hydrogen
evolved by the action of the acid upon the galena may be employed in the manu-
facture of sulphuric acid or other useful purpose.-The zinc used in this process is
readily recoverable by well known chemical ineans.-According to another process
the galena is roasted in a limited supply of air sulphurous anhybride being liberated
the residue is then treated with hydrochloric acid which decomposes any residual
sulphide of lead and the mixture of chloride and sulphate of lead thus obtained is
then extracted with a solution of brine which dissolves both the chloride and the
sulphate of lead and from the extract the porous lead is precipitated by means of
zine or spelter as already described.-The sulphurous anhydride liberated in this
process may also be employed for the manufacture of sulphuric acid or other useful
purposes. If the galena contains besides lead foreign substances such foreign sub-
stances should be removed the object being to get the lead as pure as possible.-The
lead as thus obtained suits our purpose admirably and may be obtained at small

page_text: cost by either of these or other similar processes direct from the ores of lead and
we claim the application of the porous lead as thus obtained direct from the mineral
sources of lead to the construction of secondary batteries or accumulators.
We now proceed to detail in accordance with the foregoing description the
instructions for constructing a battery say of 10 compound cells each cell being
composed say of 8 elements or 4 pairs.-It will be understood that these instructions
may be modified in various way and are only given by way of illustrating clearly
one method of proceeding to carry out the Invention
A rod or plate of some conductor say lead or carbon is taken and around the
greater part of its length is moulded gently with the hands a quantity say weighing
16 ozs. of our specially prepared porous lead which is kept if necessary in its place
for the moment by cotton or thread. Thus prepared the pole so to call it is sus-
pended or made to stand upright in the centre of a suitable mould (say of a flat
character having parallel sides) into which is then poured a mixture in the propor-
tion of say 48 ozs. of red lead (or other lead compound such as the sulphate) and
8 ozs. of plaster of Paris or of the other materials above mentioned and capable of
setting and sufficient water to make it into a thin paste: when the said mixture
has set the whole apparatus is removed from the mould and constitutes one
element. Then seventy nine other elements are similarly constructed, after which
they are placed in suitable cells or containing vessels to the number of 8 elements
in each cell, being placed side by side either cemented together by pure plaster of
Paris or else isolated by means of a strip of gutta percha or wood between each
element: The containing cell or vessel is charged with sulphuric acid and water
say in the proportions of 1 part strong acid to 9 parts of water and the 8 several
terminals of the elements are then alternately connected or bound up thus forming
a compound pair of each of the 10 cells.-To obtain tension effects the various cells
may be connected as is well known.-If the conducting terminals be made of lead
or other metal liable to be acted upon and slowly destroyed by the action of the
acid and other agencies, they may be protected from such effects where necessary by
means of a coating of gutta percha or other material which is not attacked by dilute
sulphuric acid.
It will be seen that the foregoing description of the manner of priming a battery
applies specially to the form of battery represented in Figure 1 but from the
description already given added to an inspection of Figures II III and IV of the
Drawings any competent workmen may readily construct a battery according to the
forms shewn respectively in Figures II. III and IV.
It will be understood of course that the relative amounts of metallic porous lead
and the compound of lead (for instance say red lead) used in constructing the two
elements of any pair may vary. For example at the positive pole we may have
either porous metal solely or red lead or other compound of lead mixed with plaster
of Paris or with the other materials above mentioned solely and at the negative
pole we may have only red lead or other compound of lead mixed with plaster of
Paris or with the other materials above mentioned solely, but when both porous
metal and the said mixture of lead compound with plaster of Paris or the other
materials above mentioned are employed at both poles we may employ a relatively
greater proportion of the lead compound mixture with plaster of Paris or other
materials above mentioned say twice as much at the positive pole.-Or again we
may employ the porous metal solely at both poles using the plaster if desired to
retain the inetal in its place against the respective terminals.
Having now described and particularly ascertained the nature of the said
Invention and the manner in which the same is or may be used or carried into
effect we would observe that what we consider to be novel and original and there-
fore claim as the Invention secured to us by the hereinbefore in part recited
Letters Patent, is :-
1
First, the use of finely divided porous lead prepared as hereinbefore described to
serve in part construction of secondary batteries.
Second, the use of plaster of Paris or other like cements china clay or other

page_text: similar carths as herein before described as a support for the active parts of secondary
batteries:
Third. The improved secondary batteries constructed substantially as herein-
before described for the storage of energy.
In witness whereof we the said John Evelyn Liardet and Thomas Donnithorne
have hereunto set our hands and seals this Twentieth day of June in the
year of our Lord One thousand eight hundred and eighty two.
J. EVELYN LIARDET. (L.S.)
THOS. DONNITHORNE. (L.S.)