Improvements in and Relating to Primary Batteries.
Year: 1896

page_text: Date of Application, 27th July, 1896
Complete Specification Left, 15th Apr., 1897-Accepted, 24th July, 1897
PROVISIONAL SPECI
TION.
Improvements in and Relating to Primary Batteries.
We, RENÉ MARIE JOSEPH HEURTEY, of 55, Rue de Chateaudun, Paris, France,
Engineer, and PIERRE GERMAIN, of 15bis, Avenue Gambetta, Auxerre (Yonne),
France, Electrician, do hereby declare the nature of this invention to be as
follows:-
Each cell of this battery consists of an outer receptacle, with double water tight
joints, constructed of hard wood, and coated on the inside and outside, and in some
cases provided with projecting ribs underneath, and closed by a screwed and
cemented cover and containing the following elements or parts enumerated in order
from bottom to top.
A sheet of zinc amalgainated on one surface, and covered on the other side and on
its edges with an insulating varnish, placed in and cemented when hot to the bottom
of the box or case.
A thin layer of cellulose impregnated with a solution of ammonium- and magnesium
chloride.
A thick compact layer of higher peroxide of manganese and of granulated
graphite, the whole mass being previously impregnated with the above mentioned
solution.
A plate of moulded carbon of special shape, which will be described later on.
A second layer of peroxide of manganese and of graphite.
A layer of cellulose similar to the first one.
A second sheet of zinc amalgamated on one side, varnished on the other and on
the edges and connected electrically with the first sheet of zinc by a plate of copper
covered with insulating varnish.
A flexible non-attackable water-tight membrane.
A rigid small board of prepared wood constituting the bottom of the spring
chamber.
The said spring chamber closed hermetically by the cover and containing a
number of small springs, symmetrically disposed about the whole active surface.
A rigid cover of hard wood screwed on to the four sides of the box and cemented.
Two metallic terminals coming out from one side of the box, and having water-
tight joints, or fittings.
When the two poles are connected, a current is obtained at the terminals of
1 volt. 60, of 2.5 amperes for a square decimetre due to the following assumed
a ctions.
The water is decomposed; the oxygen, freed at the contact with zinc, oxidises the
latter. The zinc-oxide reduces the ammonium and magnesium chloride; and
oxy-chloride of zinc free ammonia and magnesia are formed. The two latter

page_text: prevent the highly-resisting crystals from adhering to the amalgamated zinc and
also prevent formation of excess of impermeable zine oxide.
Hydrogen which has become free at the contact with the grains of the graphite
and peroxide of manganese, reduces the latter. Steam and saline oxide of manganese
(manganate of manganese) is formed, which is a better conductor than the sesqui-
oxide of the Lechlanche cell. Afterwards this manganate is itself reduced to a
sesquioxide with a lowering of the power of the cell which corresponds to the
last period of action of the latter..
The outer receptacle of hard wood, in order to resist rupture and corrosion from
the outside, must be perfectly watertight which is attained by compressing liquid.
glue or cement in the joints at the moment it is nailed down or secured. Covering
the mass with bot parafline and the application of an elastic coating which will
not crack, are indispensable complements for attaining water-tightness. The cover
is screwed on, the said elastic conting being interposed.
The watertight membrane and the plate forming the bottom of the spring chamber,
are joined to the sides of the box by caoutchone paste affording a watertight and
elastic joint.
The joints between the two terminals and the box are hermetic, the slightest crack
would have the double inconvenience of allowing the exciting liquid to escape and
corrode the metal, and to evaporate from the interior.
In certain cases there are arranged ribs on the bottom of the receptacle in order to
better insulate the cell and to prevent the diffusion of the current in the mass.
The action of the springs is very much subdivided in order to obtain a good dis-
tribution of pressure and the most perfect adherence between all the points of the
surface of the zinc and of the cellulose. It is found moreover that the subdivision of
the action of the springs prevents accidental breaking of the carbon plate, when the
receptacle is closed under pressure, and also in all accidents of shocks and knocks.
Furthermore it produces progressive compression of the mass.
These springs by their pressure establish contact between the layers of the cella-
lose and the zines so that air cannot enter and free mercury cannot escape; the
surface of the electrodes is always in contact with the liquid and the maximum of
conductivity of the mass of the granular depolariser is attained without interposition
of insulating sticky substances melted or softened by heat.
The very thin plates of pure laminated zinc are amalgamated on the active surface
and varnished on the other side and on the edges.
They are applied exactly over the cellulose nuassed suitably for the purpose and
taking their shape by elasticity.
The plate at the bottom of the box is cemented on with appiication of heat and
thus attached to the box.
The two zinc plates of the same cell are rivetted to an inner conductor which is in-
sulated by a varnish and a thick layer of paste covered with caoutchouc and protected
by a semi-cylinder of a non-conducting material. A screw threaded rod in close con-
tact with said conductor traverses the side of the box and is held there by a nut and
constitutes a terminal. This arrangement permits the use of only one terminal for
two plates and ensures a perfect watertightness.
The positive electrode consists of a strong carbon plate which has been several
times successively tempered and burnt, coated with paraffine at a high temperature,
with a metallic terminal attached to one of its extremities in the time when it is
moulded it presents round the metallic rod an increased thickness forming a collar
on which rests a caoutchouc washer. The metallie rod alone passes through the box
and an outer nut compresses the caoutchoue strongly and forms a perfectly tight
joint.
The carbon plate is impregnated with paraffine in order to protect the metallic rod
against the corrosive action of the active liquids.
The exciting liquid is used in a concentrated cold state. It impregnates the
cellulose layers and the grains of peroxide of maganese and graphite.
In the layer of the cellulose placed under the pressure of the springs an excess of

page_text: liquid would be injurious, if before preparing this layer this excess of liquid were not
excluded and if all air contained in the cellulose had not been carefully eliminated.
The grains of peroxide of manganese and of graphite impregnated to saturation.
with the exciting liquid and containing salt in crystalline condition are thoroughly
mixed and heaped in regular order.
The vegetable absorbent cellulose is also saturated with the exciting liquid.
Among the different varieties of cellulose such are chosen which, like the cellulose
of cocoa nut and of rush retain the inost liquid under pressure, are the least subjected
to decomposition or putrefaction and are easy to separate from the bodies with which
they are impregnated, and are capable of being heaped or inassed regularly.
The smooth and flat layer of cellulose on which the zinc plate rests, retains all its
physical properties during the life of the cell, and is inert.
The cellulose of which the layer consists taken for instance from the light casing
of the monoecious cocoanut, is separated at first from the hard wooden shell of the
nut and then from the long fibres, used in brush and mat making.
Rotary combs of tempered steel may be used for separating the raw cellulose from
the long fibres.
The raw cellulose is composed of small fibres and of grains of very different sizes.
It is exposed for some time to the combined action of water and air by placing it in
a heap, or after having wetted it in order to facilitate the transformation or reinoval
of tannic substances, the coloured liquid retained by the light stuff is pressed out be
means of a press.
The pressed stuff is at once submitted to several successive operations of sieving
through coarse meshes under pressure. In these operations a large quantity of short
fibres is separated from the granular stuff.
It is then dried and passed through a sieve. Nearly all she small fibres are
eliminated and the cellulose of heterogeneous granulation is collected.
The crushing of the coarse cellulose presents certain difficulties.
If the cellulose obtained does not resist sufficiently the chemical agents, it is on
account of the infinitisimal layer of cerosine or wax which covers the walls of the
cells not being sufficient, the cellulose is then subjected to an impregnation with
cerosine in the state of vapor as in vulcanisation.
All vegetable cellulose of any other origin than that of the monoecious cocoa-nut
such as rushes, marrow, down of gossypuim crowns of mushrooms or fungus and
generally any light cellulose, the cells of which are not impregnated with cerosine or
other fat substances, will also have to be subjected to the above treatment.
The receptacle forming the battery cell being of hard wood well joined together
with double mortise is very portable. By nailing down the sides, by screwing the
cover with the interposition of plastic glue or cement in the joints, and by sprending
inside an impervious elastic coating, a necessary tightness is attained for preventing
any admission of air or evaporation of the contained liquid.
Moreover, the absolute rigidity and the non-deformation of the walls permits the
utilisation of all the pressure localised under the cover over all parts of the cell.
The terminals by their tight joints prevent the corrosive action of the active liquid
form being exercised on thein.
The use of a mechanical press for putting on or securing the cover over the springs
allows of a simultaneous adjusting, cementing and screwing of the said cover on the
four sides of the receptacle.
The action of the subdivided multiple springs being well distributed, the inner
resistance is diminished, the carbon is preserved from breakages, and the electrolytic
functions are made inore regular. The springs themselves cannot be deformed. The
spring chamber preserves them from oxidation, from corrosion and from any similar
cause of weakness.
The active liquid is constantly brought in contact with the electrodes.
The small particles of mercury becoming free in consequence of the dissolution of
neighbouring molecules of zine under the influence of the pressure and of the
sieving action of the cellulose combine again with lower molecules.

page_text: The electromotive force remains much more constant for an equal quantity o
current than in cells having analogous reactions.
The internal resistance is considerably diminished and remains more uniform.
The liquids cannot escape from the cells, the cells being perfectly secure
whether fixed or moving.
It is at once a cell of quantity and of tension and can replace all other cells.
It does not require any maintaining, is very clean and does not evolve any
gases.
Dated thi. 07.h
1000
BOULT & WADE,
Agents for the Applicant.
COMPLETE SPECIFICATION (AMENDED).
Improvements in and Relating to Primary Batteries.
We, RENE MARIE JOSEPH HEURTEY, of 55, Rue de Chateaudun, Paris, in the Republic
of France, Engineer, and PIERRE GERMAIN, of 15bis Avenue Gambetta, Auxerre
(Yonne) in the Republic of France, Electrician, do hereby declare the nature of
this invention and in what manner the same is to be performed to be particu-
larly described and ascertained in and by the following statement:-
Each cell of this battery consists of an outer receptacle, A, having water-tight
joints, constructed of hard wood and coated on the inside and ontside and in some
cases provided with projecting ribs underneath and closed by a screwed and cemented
cover and containing the following elements or parts enumerated in order from
bottom to top ;-
1. A sheet of zinc, B, amalgamated on one surface, and covered on the other side
and on its edges with an insulating or protective varnish, placed in and cemented
when hot to the bottom of the box or case.
2. A thin layer of cellulose, C, impregnated with a concentrated solution of
ammonium-magnesium chloride.
3. A thick compact layer, D. of dioxide of manganese and of granulated
graphite, the whole mass being previously impregnated with the above mentioned
solution.
4. A plate of moulded carbon, E, preferably of rectangular cross section, provided
preferably, with a boss in which is secured a screw threaded metal rod E.
5. A second layer, F, of dioxide of manganese and graphite.
6. A layer of cellulose, H, similar to the first one.
7. A second sheet, I, of zine amalgamated on one side, varnished on the other and
on the edges and connected electrically with the first sheet of zinc by a plate of copper
covered with insulating varnish.
8. A flexible non-attackable watertight membrane, K.
9. A rigid board, L, of wood impregnated with melted paraffine constituting the
bottom of the spring chamber, M.
The said spring chamber is closed hermetically by the cover and contains a number
of small springs, N, symmetrically arranged.
10. A rigid cover, O, of hard wood cemented and screwed on to the four sides of
the box.
Two metallic terminals extending out from one side of the box and having
watertight joints or fittings.
When the two poles are connected, a current is obtained at the terminals of
1 volt. 60, of 2-5 amperes per square decimetre due to the following assumed
reactions; -

page_text: The water is decomposed and the oxygen freed at the contact with zine, oxidises
the latter. Tie zine-oxide reduces the ammonium and inagnesium chloride; and
oxychloride of zine free ammonia and magnesia are formed. The two latter prevent
the highly resisting crystals from adhering to the amalgamated zinc and also prevent
formation of excess of impermeable zinc oxide.
Hydrogen which has become free at the contact with the grains of the graphite
and dioxide of manganese, reduces the latter. Water is formed, and the dioxide of
manganese is gradually reduced to sesquioxide which corresponds to the last period
of action of the cell.
The outer casing of hand wood in order to resist rupture and corrosion from the
outside, must be perfectly watertight, which is attained by applying liquid glue or
cement to the joints at the time they are made. A covering of hot paraffin and
the application of an elastic coating which will not crack should also be applied
to ensure water-tightness.
The cover is screwed on, the said elastic coating being interposed.
The watertight membrane and the place forming the bottom of the spring
chamber are joined to the sides of the box by caoutchouc paste or solution affording
a watertight and elastic connection.
The joints between the two terminals and the box must be perfect; the slightest
crack would have the double inconvenience of allowing the exciting liquid to
escape and corrode the metal, and to evaporate from the interior.
In certain cases, ribs are arranged on the bottom of the receptacle in order to
better insulate the cell and to prevent loss of current to earth, should the insulation
be defective.
A number of springs are used in order to obtain a good and equal distribution of
pressure all over the plate to produce the most perfect contact between the whole
surface of the zine and of the cellulose. It is found moreover that the use of a
number of symmetrically arranged springs prevents accidental breaking of the earbon
plate when the cover is put on the receptacle or in the case of shocks and knocks or
accidents. Furthermore progressive compression of the mass is produced.
These springs by their pressure keep the layers of the cellulose and the zines in
close contact so that air cannot enter and free mercury cannot escape, the surface of
the electrodes is always in contact with the liquid, and the maximum conductivity of
the mass of the granular depolariser is attained without the interposition of insulating
sticky substances, melted or softened by heat.
Very thin plates of pure laminated zinc are used and are amalgamated on the
active surface and varnished on the other side and on the edges.
The plate at the bottoin of the box is cemented to the bottom and thus attached
to the box.
The two zinc plates of the same cell are rivetted to an inner conductor which is
insulated by a varnish and a thick layer of paste covered with caoutchouc and pre-
ferably protected by a semi-cylinder of a non-conducting material P. A surew-threaded
rod in close contact with said conductor passes through the side of the box, and is
held there by a nut and constitutes a terminal. This arrangement permits the use
of only one terminal for the two plates and facilitates a perfect water-tightness.
The positive electrode consists of a strong carbon plate which has been several
times successively impregnated with or dipped into tar and burnt and coated when
at a high temperature with paraffine and is provided with a metallic terminal
attached to one of its extremities preferably at the time when it is moulded. Round
the metallic rod it is of an increased thickness formning a collar on which rests a
caoutchouc washer, Q. The metallic rod passes through the box and an outer nut
compresses the caoutchouc strongly and forins a perfectly tight joint.
A coating of paraffine or the like protects the metallic rod against the corrosive
action of the active liquids.
The exciting liquid is used in a concentrated cold state. It impregnates the
cellulose layers and the grains of dioxide of manganese and graphite.

page_text: In the layer of the cellulose under the spring pressed board any excess of liquid
would he injurious so that before securing this layer any excess of liquid should be
removed and air contained in the cellulose should be carefully eliminated.
The grains of dioxide of manganese and of graphite saturated with the exciting
liquid and containing salt in crystaline condition are thoroughly mixed and heaped
in a regular order.
The vegetable absorbent cellulose is also saturated with the exciting liquid.
Among the different varieties of cellulose such are chosen which like the cellulose
of cocoa nut and of rush retain the most liquid under pressure, are the least subjected
to decomposition or putrefaction and are easy to separate from the bodies with which
they are impregnated and are capable of being heaped or massed regularly.
The smooth and flat layer of cellulose on which the zine plate rests, retains all its
physical properties during the life of the cell and is in itself inert.
The cellulose of which that layer consists, taken for instance from the light casing
of the monoecious cocoanut is first separated from the hard wooden shell of the nut and
then from the long fibres used in brush- and mat-making.
Rotary combs of tempered steel may be used for separating the raw cellulose from
the long fibres.
The raw cellulose is composed of small fibres and of grains of very different sizes.
It is exposed for some time to the combined action of water and air by placing it in
a heap or after having wetted it in order to facilitate the transformation or removal
of tannic substances, the coloured liquid retained by the light stuff is pressed out by
means of a press.
The pressed stuff is then submitted to several successive operations of sieving
through coarse meshes. In these operations a large quantity of short fibres is
separated from the granular stuff.
It is then dried and passed through a sieve. Nearly all the small fibres are
eliminated and the cellulose of varying granulation is collected.
The crushing of the coarse cellulose presents certain difficulties.
If the cellulose obtained does not resist sufficiently the chemical agent, it is on
account of the infinitesimal layer of cerosine or wax which covers the walls of the cells
not being sufficient, the cellulose is then subjected to an impregnation with cerosine
in the state of vapour as in vulcanisation.
All vegetable cellulose of any other origin than that of the monoecious cocoa-nut
such as rushes, marrow, down of gossypuim crowns of mushrooms or fungus and
generally any light cellulose, the cells of which are not impregnated with cerosine
or other fat substances, will also have to be subjected to the above treatment before
use.
The receptacle forming the battery cell being of hard wood well joined together is
very portable. By nailing down or screwing the sides, by screwing the cover with the
interposition of plastic glue or cement in the joints, and by giving the inside an
impervious elastic coating any admission of air or evaporation of the contained liquid
is prevented.
Moreover the absolute rigidity and fixity of the walls permits the utilisation of the
spring pressure over all the parts of the cell.
The terminals by their tight joints prevents the corrosive action of the active liquid
from being exercised on them.
A mechanical press may be employed for putting on or securing the cover over the
springs to allow of a simultaneous adjusting cementing and screwing of the said cover
on the four sides of the receptacle.
The action of multiple a number of springs being well distributed the innerresistance
is diminished, the carbon is preserved from breakages and the electrolytic functions are
made more regular. The springs themselves do not become deformed and the spring
chamber preserves them from oxidation, from corrosion and from any anticipated
cause of weakness.
The active liquid is constantly brought in contact with the electrodes.

page_text: The small particles of mercury becoming liberated in consequence of the dissolution
of neighbouring molecules of zinc, are prevented from leaving the surface of the zine
by the pressure of the layer of cellulose, and so become re-analgamated with the
zinc.
The electromotive force remains inuch more constant for an equal quantity of
current than in cells having similar reactions.
The internal resistance is considerably diminished and is very uniform.
The liquids cannot escape from the cells, the cells being perfectly secure whether
fixed or moving.
The battery does not require any further maintaining, is very clean and does not
give off any gases.
Owing to the close and intimate contact of the zinc with the cellulose saturated
with the electrolyte as the zinc is consumed and the mercury liberated, it again
becomes amalgamated the mercury not being precipitated as in other form of
batteries.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed we declare that what
we claim is :-
1. An-electric-battery cell constructed of hard-wood-rendered-air-and-liquid-
tight-in-the-munner-described and-having its joints glued together-and conted;-the
over-being-pressed-on-by-means-of-mechanical pressure and serewed under pressure,
-couting being applied at the joints substantially as described.
2. In-an-electric-buttery-of the character-described terminals inserted-in-the-walls
of the cell-in an air and liquid tight munner, one-of-them-being--connected to an
intermedinte-insulated and protected-red connecting the two-zine plates of the cell
substantially-us-described.
1. In an electric battery of the character described the use of multiple a number
of springs to compress the elements of the battery in an air-tight chamber, the
springs being protected against injury from the elements by an impermeable elastic
membrane substantially as described.
In-un-electric buttery of the character described the progressive kneading-of
the lower--cellulose layer of the-mixture of dioxide-of-manganese-and-graphite
surrounding the wurbon-electrode, and of the upper layer of cellulose, the whole
being gradually-pressed together-before-final elesing of the cell-substantially-us
described.
. . In an electric battery a device for obtaining a constant elastic pressure on
the depolarising material, in order to obtain a greater electric conductibility without
using a porous vessel or binding material, substantially as described.
63. In a primary electric battery of the character described the use of a con-
centrated solution of double chloride of aminonium and magnesium saturating a
layer or layers of cellulose and the depolarising material substantially as and for the
purpose described.
7. In a primary-electric buttery the use of n-lover-or-layers-of-cellulose saturated
with double chloride-of-ammoniain-and-magnesium placed-between-a-zine plate-and
the depolarising material-substantially-us-described.
4. In an electric battery two layers of mixed grains of dioxide of manganese
and graphite, saturated with the electrolyte and surrounding the carbon-electrode,
the whole constantly pressed together by means of springs substantially as described.
0. In an electric battery the use of a positive carbon electrode treated with
puraflin-at-a high-temperature-and--having-a-metallic terminal inserted into it-at
the time-of-moulding und-projecting through-the-cell, the air and liquid-tightness
being ensured by means of an elastic insulating-washer and-mut-substantially-as
described.
10. In-an electric battery the employment-of-an amalgamated sine plate-in-inti-
mate-contact-with-a-layer of cellulose impregnated with-the-electrolyte, whereby

page_text: Buttertes.
the particles-of-amalgam-ns-they-become-liberated,-are--maintained in contact with
the-zine-and-so-effect-a-re-malgamation of the zine-substantially-as-described.
5. In an electric battery the use of absorbent, elastic, inert, non-decomposing
cellulose, prepared so as to be freed from tannin, and possessing so as to possess great
power of absorbing liquids and gases, substantially as and for the purpose described.
16. The combination and arrangement of parts constituting the complete
primary electric battery substantially as described.
Dated this 31st day of March 1897.