Improvements in and relating to Dry and other Galvanic Batteries.
Year: 1892

page_text: Date of Application, 16th Sept., 1892
Complete Specification Left. 26th Apr., 1893-Accepted, 17th June, 1893
PROVISIONAL SPECIFICATION.
Improvements in and relating to Dry and other Galvanic Batteries.
I, ALFRED ERNEST JOSEPH BALL of West Hooe near Plymouth Watch &
Clock Maker do hereby declare the nature of this invention to be as follows:-
This invention relates to an improved electrolyte and improvements in batteries
for the use of same. It is well known to those conversant with the subject to
which my improvements refer that the solution of sal-ammoniac as generally used
in the Leclanché and other similar types of batteries-also as the excitant in dry
cells when subjected to hard work or changes of temperature, is very liable to
crystallise on the zinc element, thereby preventing chemical action on the zinc and
consequently preventing, or at all events materially retarding the battery or cell
from producing the electric current; moreover the said solution is subject to what
is technically known as "creeping." Now the object of this invention is, mainly,
to remedy these defects.
"
In proceeding to carry out my invention, I employ an improved exciting solution
or electrolyte which I produce by dissolving about equal proportions of CaCl2
(calcium chloride) ZnCl2 (zinc chloride) and NH C1 (ammonia chloride) in pure
water. I have found that this mixture does not crystallise and that it does not
appear to have any tendency to "creeping; and as these ingredients are very
soluble, almost any strength of solution may be obtained. Hard water containing
CaCO, (calcium carbonate) (spring water from limestone districts) should not be
used, but should this user be unavoidable the deposit of the CaCO3 on the negative
element (carbon electrode) can be prevented by surrounding the said element
with a paste of CaSO, (calcium sulphate) with or without the addition of a little
powdered sulphur.
Whilst specifying the proportions of the three chlorides in my improved
electrolyte to be about equal, I wish it to be understood that I do not confine
myself to any exact proportions of the ingredients, but in practice I obtain the
best results from the following proportions:-CaCl, one and a half parts (if the
recrystallized be used two and one fourth parts) ZnCl, one part, NH Cl one and a
half parts, pure water twelve parts. The ZnCl, I use the least in proportion of,
relatively to the other chlorides, chiefly because more of this compound is produced
while the cell is in action.
The function of the NH4Cl appears to be chiefly that of a solvent; for its
presence in the mixture enables a larger quantity of the two other chlorides to be
obtained in the form of a solution.
On account of the great hygroscopic properties of my improved electrolyte
(CaCl, being one of the most hygroscopic of the known deliquescent salts) and as
it does not crystallise, it is eminently adapted for use in galvanic dry cells or
batteries seeing that highly deliquescent salts are most suitable for the purpose as
they retain their humidity.
In order that my improved electrolyte may acquire the necessary stiffness or
consistency, I first thicken it by the addition of gélatine (preferably Russian) in
the proportion of about one part of gelatine to ten parts of the solution I then
introduce and stir in, plaster of paris in the proportion of about two parts thereof
to one part of the solution, so as to convert it into a pulp-like mass which will set
in a few hours to about the consistency of stiff dough.
Another method I sometimes adopt for imparting the requisite consistency and
by which equally good results are obtained, is to employ less gelatine and to make
up for this reduced quantity of the latter, by using a small quantity of flour; or,

page_text: may use an increased proportion of flour and no gelatine, the function of the flour
gelatine or the like being simply to tone down the plaster of paris and prevent it
from setting too hard.
To construct my dry cells I proceed as follows :-
make a zinc vessel or cell of suitable shape and solder to it a suitable terminal
or wire and if the cell is for use in damp situations, I isolate it by fixing to its
bottom a disc or block of ebonite, glass or other similar insulating material of
suitable shape to constitute an insulating base, by preference I amalgamate the
inside of cell and place into it the negative element (isolated) which I construct
of a carbon plate or rod (having terminal attached) surrounded with a depolarizing
mixture (compressed around carbon plate by a mould or enclosed in a calico
wrapping) consisting of peroxide of manganese and plumbago or carbon, the said
mixture having one or more cores of absorbent material such as cotton, for
promoting circulation, running through it say from top to bottom and communi-
cating with the exciting mass at both ends. I then fill in the space between the
inside of the zinc cell and the negative element with my improved electrolyte
mixed with gelatine or the like and plaster of paris as above described, leaving
sufficient space for the sealing. When this latter has set-which will occur in
the course of a few hours-I seal up the cell as follows:-
I first seal over the exciting mass with a layer of wet plaster of paris which
quickly sets over this place a shallow gas-drying chamber made of some non-
conducting material and filled with saw-dust or similar absorbent and having its
under surface (next the plaster seal) perforated (the perforations to constitute
ventilating holes) and its upper surface fitted with a short glass or ebonite tube
which should stand or project a little above the level of the zinc cell. The space
above the said chamber I fill in with a final seal of some dense non-porous material
such as pitch or pitch with a small admixture of paraffin wax or other substance
to render it less brittle.
By thus arranging the gas-drying chamber above the exciting mass, the moist
electrolyte carried or driven away by the undepolarised hydrogen (produced by
excessive work or other causes) has an opportunity of again reaching the exciting
mass by gravitating into it on a favorable opportunity presenting itself, that is to
say, on the subsidence of the gas.
Moreover the arrangement I have described, has the advantage of economizing
space, it does not make the cell "bulky," whilst in practice it is found to be of
sufficient capacity and has not a tendency in any way, when charged with moisture,
to short circuit the cell.
Dated this 15th day of September 1892.
COMPLETE SPECIFICATION.
Improvements in and relating to Dry and other Galvanic Batteries.
I, ALFRED ERNEST JOSEPH BALL of West Hooe near Plymouth Watch and
Clock Maker, 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 :-
This invention relates to an improved electrolyte and improvements in batteries
for the use of same. It is well known to those conversant with the subjects to
which my improvements refer that the solution of sal-ammoniac as generally used
in the Leclanché and other similar types of batteries, also as the excitant in dry
cells when subjected to hard work or changes of temperature, is very liable to
crystallise on the zinc element thereby preventing chemical action on the zinc and
consequently preventing or at all events materially retarding the battery or cell

page_text: from producing the electric current; moreover the said solution is subject to what
is technically known as creeping."
«
Now the object of this invention is, mainly, to remedy these defects.
In proceeding to carry out my invention, I employ an improved exciting solution
or electrolyte which I produce by dissolving about equal proportions of CaCl2
(calcium chloride) ZnCl, (zinc chloride) and NH.CI (ammonium chloride) in pure
water. I have found that this mixture does not crystallise and that it does not
appear to have any tendency to creeping;" and as these ingredients are very
soluble, almost any strength of solution may be obtained. Hard water containing
CaCO, (calcium carbonate) (spring water from limestone districts) should not be
used, but should this user be unavoidable, the deposit of the CaCO3 on the negative
element (carbon electrode) can be prevented by surrounding the said element with a
paste of CaSO, (calcium sulphate) with or without the addition of a little powdered
sulphur.
Whilst specifying the proportions of the three chlorides in my improved
electrolyte to be about equal, I wish it to be understood that I do not confine
myself to any exact proportions of the ingredients, but in practice I obtain the best
results from the following proportions
:-
CaCl, one and a half parts, (if the recrystallized be used two and one fourth
parts) ZnCl, one part, NH.C1 one and a half parts, pure water twelve parts.
The ZnCl, I use the least in proportion of, relatively to the other chlorides,
chiefly because more of this compound is produced while the cell is in action.
The function of the NHCl appears to be chiefly that of a solvent; for its
presence in the mixture enables a larger quantity of the two other chlorides to be
obtained in the form of a solution.
On account of the great hygroscopic properties of my improved electrolyte
(CaCl, being one of the most hygroscopic of the known deliquescent salts) and as
it does not crystallise, it is eminently adapted for use in galvanic dry cells or
batteries seeing that highly deliquescent salts are most suitable for the purpose as
they retain their humidity.
In order that my improved electrolyte may acquire the necessary stiffness or
consistency, I first thicken it by the addition of gelatine (preferably Russian) in
the proportion of about one part of gelatine to ten parts of the solution. I then
introduce and stir in plaster of paris in the proportion of about two parts thereof
to one part of the solution, so as to convert it into a pulp-like mass which will set
in a few hours to about the consistency of stiff dough.
Another method I sometimes adopt for imparting the requisite consistency and
by which equally good results are obtained, is to employ less gelatine and to make
up for this reduced quantity of the latter, by using a small quantity of flour; or I
may use an increased proportion of flour and no gelatine, the function of the flour,
gelatine or the like being simply to tone down the plaster of paris and prevent it
from setting too hard.
To construct my dry cells I proceed as follows:-
I make a zinc vessel or cell of suitable shape and solder to it a suitable terminal
or wire and if the cell is for use in damp situations I isolate it by fixing to its
bottom a disc or block of ebonite, glass or other similar insulating material of
suitable shape to constitute an insulating base, by preference I amalgamate the
inside of cell and place into it the negative element (isolated) which I construct of
a carbon plate or rod (having terminal attached) surrounded with a depolarizing
mixture (compressed around carbon plate by a mould or enclosed in a calico
wrapping) consisting of peroxide of manganese and plumbago or carbon, the said
mixture having one or more cores of absorbent material such as cotton, for
promoting circulation, running through it say from top to bottom and communicating
with the exciting mass at both ends. I then fill in the space between the inside of
the zinc cell and the negative element with my improved electrolyte mixed with
gelatine or the like and plaster of paris as above described, leaving sufficient space

page_text: for the sealing. When this latter has set,-which will occur in the course of a few
hours, I seal up the cell as follows:
I first seal over the exciting mass with a layer of wet plaster of paris which
quickly sets; over this I place a shallow gas drying chamber made of some non-
conducting material, and filled with saw-dust or similar absorbent and having its
under surface (next the plaster seal) perforated (the perforations to constitute
ventilating holes) and its upper surface fitted with a short glass or ebonite tube
which should stand or project a little above the level of the zinc cell. The space
above the said chamber I fill in with a final seal of some dense non-porous material
such as pitch or pitch with a small admixture of paraffin wax or other substance to
render it less brittle. By thus arranging the gas drying chamber above the
exciting mass the moist electrolyte carried or driven away by the undepolarised
hydrogen (produced by excessive work or other causes) has an opportunity of again
reaching the exciting mass by gravitating into it on a favorable opportunity
presenting itself, that is to say, on the subsidence of the gas. Moreover, the
arrangement I have described, has the advantage of economizing space, it does
not make the cell "bulky” whilst in practice it is found to be of sufficient capacity
and has not a tendency in any way, when charged with moisture, to short-circuit
the cell.
Referring to the annexed drawings;
Figure 1 shews a vertical section of the dry battery according to my invention;
Z being the zinc cell and containing vessel, W being the connection wire: B shews
a metallic post constituting an advantageous method of connecting said wire to
zinc cell, I is the insulating base, C the carbon plate and T the terminal, A being
the absorbent core for permitting access of the electrolyte through the depolarizing
mass and enabling the cell to maintain its maximum E.M.F. (electro motive force)
D is the depolarizing mixture and L the wrapping with which the same is
enveloped. E is the improved electrolyte herein before referred to mixed with the
stiffening materials as herein before set forth, P is the plaster of paris seal and
G the gas-drying chamber; S being the sawdust or similar material, V the
ventilating holes and F the tube for the purpose of conducting away the gases.
H is the final seal of pitch or other non-porous material.
Figure 2, shews a side elevation of the carbon plate fitted with the absorbent
core, C being the carbon, A the absorbent core and T the terminal.
Figure 3, shews a sectional elevation of a modified cell device which ensures a
high degree of lightness without reducing its active surface in proportion and is
intended for purposes where a cell of light weight is desired. It consists of an
inner cylinder of zinc, placed within an outer cylindrical vessel or cell of carbon,
the space between the two being filled in with the exciting mass.
The carbon may
be agglomerated with peroxide of manganese, or its inner surface coated with the
depolarizing mixture, C shews the carbon cylinder or containing cell E the exciting
mass, Z the zinc cylinder, H the scaling, T the terminal and W the connection
wire, a shews the air space by reason of which the cell is rendered light in weight.
The chemical changes which take place in my improved cell appear to be the
same as those which occur in the well known Leclanché type of cell, accompanied
by the additional changes represented by the equation
Zn + CaCl₂ =
ZnCl2 + Ca.
Having now particularly described and ascertained the nature of my said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is:
(1) A galvanic battery electrolyte for use in dry and fluid galvanic cells,
consisting of calcium chloride, zinc chloride, ammonium chloride and water as
described.
(2) In a dry cell, the use of absorbent cores running through the depolarizing
mass, as and for the purposes herein set forth.

page_text: (3) In a dry cell the use of a gas-drying and ventilating chamber and arrange-
ment as berein set forth and shewn.
(4) An insulating base for galvanic batteries as set forth and shewn.
(5) In a dry cell the metallic post B, fixed to the zinc element Z, to carry the
wire W, substantially as described and shewn.
ALF. E. J. BALL.