IMPROVEMENTS IN THE CONSTRUCTION OF VOLTAIC BATTERIES
Year: 1883

page_text: LETTERS PATENT to Arthur Charles Henderson of 47 Museum Street Oxford
Street in the Parish of Bloomsbury and county of Middlesex for an Invention
of IMPROVEMENTS IN THE CONSTRUCTION OF VOLTAIC BATTERIES communi-
cated to him from abroad by Nicolas Basset Chemist of the city of Paris in
the Republic of France
PROVISIONAL SPECIFICATION left by the said Arthur Charles Henderson
at the Office of the Commissioners of Patents on the 4th October 1883.
ARTHUR CHARLES HENDERSON of 47 Museum Street, Oxford Street, in the
" IMPROVEMENTS IN THE
parish of Bloomsbury and county of Middlesex
CONSTRUCTION OF VOLTAIC BATTERIES A communication to me from abroad by
Nicolas Basset, Chemist of the city of Paris in the Republic of France
"
The improvements referred to consist in an economical method of constructing
voltaic couples or elements yielding a primary, constant, and intense current, also
in the formation of secondary elements for completing the work of the primary
couples, and accumulating and storing the product of these elements.
The primary elements consist of zinc and carbon couples with double liquid
arrangement, separated by a diaphragm or porous cell of minimum resistance.
The conducting liquid on the zinc side is a solution of alkaline chlorid more or less
concentrated, alkalized or not, and of a density equal to that of the exciting fluid
of the carbon side, this latter is a solution of double salts whose formula is
Mn CL. Fe Cl³ which becomes Mn Cl, (Fe Cl) by loss of an equivalent of chlorine
which is taken up by the zinc.
Dechloridizing may be carried to the extreme limit, but it is best in practice not
to reduce the chlorid Fe Cls beyond its transformation to protochlorid.
The electro-motive force of this element is 1 Daniell 25 and is constant if the
strength of the element is maintained. The loss with an open circuit is reduced to a
minimum In maintaining this strength a little of the liquid from the zinc side is
withdrawn from time to time, and replaced with the alkaline chlorid solution
keeping up its density.

page_text: At the carbon side a little of the liquid is removed when it has become of an
olive green shade and crystals are added of Mn Cl Fe³ Cl³ prepared as hereafter
described
The strength of the element may be maintained by any of the usual methods, or
by simple circulation of the liquids.
With regard to the electro-motive force in certain cases of alkalization of the
chlorid produced by adding to the solution of K Cl or Na Cl. to of soda,
this addition raises the electro-motive force to Daniell; this alkalinity being
maintained, the alkali first passes to the state of chlorid before the zinc is
chloridized by the current.
The preparation of the exciting liquid Mn Cl Fe³ OP is as follows: The process
or preparation of Fe Cl is well known, it sufficing in the first instance to dissolve
together the equivalents of each of the two salts. But the preparation of the
sesqui-chlorid of iron by the action of azotic acid or by chloric acid is disagreeable
and inconvenient and less economical, preference is therefore given to another
method after having prepared the solution of protochlorid of iron Fe Cl. by the
action of chloridic acid on old iron parings or chips, the protochlorid is heated
with powdered peroxyd of manganese, adding 'by degrees the chloridic acid till it
reaches the formula Mn O2 + 2 (Fe Cl) + 2 H Cl = Mn Cl Fe C³ + 2 H O.
This process obviates the employment of azotic acid, the chlorine being absorbed
as quickly as it is liberated by Fe Cl and the manganese, so that the preparation is
easily effected.
As it is advantageous to feed the pile with crystals, or at least with crystalline
paste; to the concentrated solution of Mn Cl Fe³ Cl³ is added a sufficient quantity
of alkaline chlorid, and evaporation is effected with boiling water, care being taken
to leave a slight excess of chloridic acid.
Renewing the agents-The conducting liquid is enriched with chlorid of zinc
which does not sensibly impair reaction: but it is best to restore it to its primary
condition. With this view it suffices to treat it with an alkaline carbonate, after
having (if desired) precipitated the iron and the manganese if in ebullition they
should accidentally come in presence of the carbonate of zinc
The oxyd or the carbonate of zinc can be sold or restored to metal either by
drying or the elecrolytic process.
From what has previously been said the exciting fluid Mn Cl Fe Cl or Mn Cl
Fe Cl³, K Cl or Mn Cl Fe Cl³ Na Cl is indefinitely re-established by boiling
some minutes on Mn O³ with the gradual addition in requisite proportions of
chloridic acid. The residue oxyd of iron and manganese is similarly restored when
dechloridizing has been carried too far.
Porous cells and diaphragms-Porous cells, vases, or diaphragms of minimum
resistance are produced in the following manner-A mixture is prepared of 30 parts
of plastic clay, 25 parts of broken crucibles or sand, 30 parts of hard coke or
plumbagin and 15 parts of sesqui oxyd of iron. These proportions should be
considered as an example only.
These matters are pulverized and passed through a fine sieve, they are thon
made into plastic paste to which the desired form is given, and after drying in the
shade these cells are then placed in an oven and are surrounded and filled with dry
sand, and are then baked to red heat. Two hours baking suffices, which should
not be prolonged, so as to prevent making them too close.
Construction of the secondary element, storage or accumulator-In forming an
electrode of a secondary element it suffices to place a conductor of some kind in
contact with one of the agents here indicated viz: oxyd of lead, any compound
oxydized with a metal, can serve as a base in the formation of a secondary battery,
provided it is susceptible of suroxydation. or reduction by the current: thus the
oxyds of manganese, of iron, of chromium, tin, lead, or antimony can be used as
well as the metallic oxyds of which there are sub oxyds, such as nickel, cobalt, zinc,
bismuth, copper, mercury, and silver, to which may be added all the combinations
of the metals with the metalloids, which can pass from an inferior to a superior

page_text: ate, by reduction or otherwise, can also be employed as a base to a secondary
lement, such as sulphurs, and mono-sulphurs or sesqui sulphurs in which the
etalloids which ever they be play the same röle as the oxygen, and the oxyds
The metal blades may be replaced by a conductor of some sort, and it suffices
hat the liquid is a conductor of the current provided it is a bad dissolvent of the
ompound employed, whether oxyd, sulphur, chlorid, bromid, or phosphorous.
In conjunction with any of these agents a conducting liquid is employed which
ither does not act, or if so very slightly on the conductor or the agent itself.
Elements therefore can be formed in several different ways by acting as above
escribed.
In a cell divided vertically in two portions by a porous division, each
ompartment is filled with a paste more or less thick, made with the agent adopted,
nd the conducting liquid, which may be a solution of alkaline chlorid or a salt
aving less action on the agent employed. In each compartment a carbon plate is
laced acting as electrode and as element.
ad The active paste is placed in two porous cells or vases each furnished with a
carbon plate, and the two cells are plunged into an external porous vase
containing the conducting liquid.
ra For the preceding porous cells, carbon cylinders are substituted, these cylinders
are filled with active paste and serve as electrodes, which are likewise placed
in a conducting liquid.
th Carbon plates separated by a cloth, felt, card or blotting paper, may be
employed, these are plunged into the conducting liquid the carbon plates
containing the active agent.
th For a conductor, a band of paper tinned, silvered, gilt, leaded, antimoniated,
or otherwise prepared is used on each side of this band are arranged one or
more sheets of blotting paper coated with the active agent and if desired a
sheet of paper steeped in paraffine The whole is fixed with strings forming a
valuable and very economical electrode.
Two of these electrodes form an element, and these two electrodes without the
nsulating sheet which separates them may be united one with the other and
lunged into the liquid separated only by the thickness of the blotting paper.
Or this kind of electrode may be made in spirals round a carbon in form of a
olumn or of vertical plates the change of form not affecting the essential
onditions herein referred to, and which form the basis of the invention.
The electrodes are arranged in a box, or trough which may be of wood, coated
r lined with wax colcothar or its equivalent, or it may be of metal similarly lined
r of glass or stone.
The electrodes of the consecutive elements may be connected for tension or
uantity. A battery of these elements can be employed and applied in all cases
where accumulators are required, with the advantage of economy and lightness.

page_text: PECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said Arthur Charles Henderson in the Patent Office on the 1st April
1884.
ARTHUR CHARLES HENDERSON of 47 Museum Street Oxford Street in the
arish of Bloomsbury and county of Middlesex IMPROVEMENTS IN THE
NSTRUCTION OF VOLTAIC BATTERIES A communication to me from abroad by
icolas Basset, Chemist of the city of Paris in the Republic of France
The improvements referred to consist in an economical method of constructing
Itaic couples or elements yielding a primary, constant, and intense current, and
the formation of secondary elements, for completing the work of the primary
uples and accumulating and storing or preserving the product of these elements
Principles resulting from experiment:
Relative to the primary current―
1st A primary couple of two liquids is useful only if it supplies an electro-
motive force E, which is constant; with a sufficient quantity or intensity I,
and with the minimum of internal resistance R
2nd It is evident that constancy cannot exist in any pile or battery, if the
liquids are not properly maintained by alimentation, or some suitable
maintenance.
3rd A good primary element should not expend in open circuit.
4th It is indispensable to avoid the production of salts that reform and collect
too rapidly on the elements or that are too coherent; and also secondary
local actions.
5th The form even of the vases or cells is accesory.
Relative to the secondary element.
6th The principle of secondary elements rests on the peroxydation of the oxyd
of lead on one of the electrodes, and its reduction by hydrogen on the other,
but the adoption of metal plates or blades for positive or negativo electrodes
has greatly increased weight, and expense, and in arresting action when the
metal plates are destroyed, and to a number of other inconveniences.
7th The above principle is correct only in so far as concerns alternate
oxydation and reduction.
8th The use of the metal blades or plates is erroneous they should only act the
part of conductors.
9th The oxyd of lead may be advantageously employed, but it is expedient to
.generalize the rule too exclusively applied to this compound. Indeed any
compound oxydized with a metal can be used as a base in the formation of a
secondary battery, provided that it is susceptible of peroxidation or reduction
by the current. Thus the oxyds of manganese, of iron, of chromium, tin, lead,
or antimony may be employed, as well as the metallic oxyds of which there is
a peroxyd, such as nickel, cobalt, zinc, bismuth, copper, mercury and silver
may be used to which may be added:-
10th All the combinations of the metals with the metalloids, which can pass
from an inferior to a superior state by reduction or otherwise, can be employed
as a base to a secondary element such as the sulphurs, and sub-sulphurs, the
chlorids, and sub-chlorids, the bi-sulphurs, and mono-sulphurs, or the sesqui-
sulphurs etc in which any of the metalloids play the same part as oxygen in
the oxyds.
11th The metal blades or plates may be replaced by a conductor of some kind,
and it suffices that the liquid should be a conductor of the current provided it
is a bad dissolvent of the compound employed, whether oxyd, sulphur, chlorid,
bromide, phosphorous etc:

page_text: C. Construction of the primary element.—The primary element consists of a zino
and carbon couple with double liquid arrangement, separated by a diaphragm.
or porous cell of minimum resistance. The conducting liquid on the zinc side,
is a solution of alkaline chlorid more or less concentrated and alkalized or not,
and of a density about equal to that of the exciting fluid of the carbon side,
this latter is a solution of double salts, whose formula is Mn, Cl, Fe², Cl³;
which becomes MD, CI (Fe, Cl) by the loss of an equivalent of chlorine, which
is taken up by the zinc. Dechloridizing may be carried to the extreme limit,
but it is best in practice not to reduce the chlorid Fe³, Cl³. beyond its
transformation to protochlorid.
The electro-motive force of this element is 1 Daniell 25, and is constant if the
strength of the element is maintained. The loss with an open circuit is reduced to
a minimum. In maintaining this strength, a little of the liquid from the zinc sido
is withdrawn from time to time, and replaced with the alkaline chlorid solution,
keeping up its density. At the carbon side a little of the liquid is removed when
it has become of an olive green shade, and crystals are added of Mn, Cl, Fe², Cl³,
prepared as hereafter described. The strength of the element may be maintained
by any of the usual methods, or by simple circulation of the liquids. With regard
to the electro-motive force, in certain cases of alkalization of the alkaline chlorid
produced by adding to the solution of K, C,1, or Na, Cl, to 1 of soda, this
addition raises the electro-motive force to Daniell, and maintains the alkalinity;
the alkali first passes to a state of chlorid, before the zinc is chloridized by the
current a certain proportion of zincate being produced: in all cases alkalization is
optional and in accordance with the results to be effected.
The external vase may be of metal provided it is lined inside with a sufficient layer
of wax and paraffined resin. Moreover I often arrange two elements in tension, or
in quantity in the same external vase, and I thus obtain a notable increase of
electro-motive force or of quantity by a phenomenon connected with the theory of
crossing two currents provided the elements do not touch.
The preparation of the exciting liquid Mn, Cl, Fe, Cl³, is as follows:-The process
of preparing Fe, Cl³, is well known, it sufficing in the first instance to dissolve
together the equivalents of each of the two salts. But the preparation of the
sesqui-chlorid of iron by the action of azotic acid, or by that of chlorine, or chloric
acid is disagreeable inconvenient and less economical, preference is therefore given
to the following method. After having prepared the solution of protochlorid of
iron Fe, Cl, by the action of chloridic acid on old iron scraps, parings, or chips, the
proto-chlorid is heated with powdered peroxyd of manganese, adding by degrees the
chloridic acid, till it reaches the formula Mn O2 + 2 (Fe Cl) + 2 H. Cl = Mn, Cl,
Fe, Cl + 2 H. O. This process obviates the employment of azotic acid, the
chlorine being absorbed as quickly as it is liberated by Fe, Cl, and the manganese,
so that it is easily prepared.
As it is advantageous to feed the battery with crystals, or at least with crystalline
paste; to the concentrated solution Mn, Cl, Fe, Cl³ is added a sufficient quantity
of alkaline chlorid, and evaporation is effected with boiling water, care being taken
to leave a slight excess of chloric acid.
Renewing the agents-The conducting liquid is enriched with chlorid of zinc,
which does not sensibly impair reaction but it is expedient to restore it to its
primary condition. With this view it suffices to treat it with an alkali or an
alkaline carbonate, after having if desired precipitated the iron and the manganese
if in ebullition they should accidentally come in presence of the carbonate of zinc.
The oxyd or the carbonate of zinc can be sold or restored to metal either by drying
or the electrolytic process. From what has been previously said, the exciting
salt Mn, Cl, Fe, Cl³, or Mn, Cl, Fe, Cl³, K. C.l, or Mn, Cl. Fe³, CI³, Na. Cl is
indefinitely re-established by boiling some minutes in Mn, 02, with the gradual
addition in suitable proportion of chloridic acid. The residue oxyd of iron and
manganese is similarly treated when dechloridizing has been carried too far.
Porous cells and diaphragms-Porous cells, vases, or diaphragms of minimum

page_text: esistance are made in the following manner-a mixture is prepared of 30 parts
f plastic clay, 25 parts of broken crucibles or sand, 30 parts of hard coke or
lumbago and 15 parts of sesqui oxyd of iron. These proportions should be
onsidered as an example only. The matters are pulverized and passed through a
ine sieve. They are then made into plastic paste, to which the desired form is
iven, and after drying in the shade, these cells are then placed in an oven, and are
urrounded and filled with dry sand and they are then baked to red heat. Two
ours baking suffices, which should not be prolonged, to prevent making them too
lose. The accompanying drawings represent examples of an element of a primary
attery constructed as described in this specification. Figs 1 and 2, show the oval
orm, in elevation and in plan. Figs 3 and 4 represent the rectangular form also
h elevation and in plan. In these figures the same letters of reference indicate
ke parts, a is the metallic electrode, zinc or iron, 6 the carbon plunged into the
xciting liquid, chlorid, protochlorid of manganese, and sesqui chlorid of iron.
he porous cell. d the external vase. ee are the feeding pipes, f f¹ the
onducting wires. The scale would be variable.
c is
D. Construction of the secondary element, storage element or accumulator:-In
forming an electrode of a secondary element, on referring to paragraphs 9. 10.
and 11 it will be seen that it suffices to place a conductor of some kind in
contact with one of the agents there indicated, and a conducting liquid, which
does not act, or very slightly on the conductor or the agent itself. I can
therefore form my elements in several different ways by acting as described
in these paragraphs.
:
1 In a cell divided vertically in two portions by a porous division, each
compartment is filled with a paste more or less thick, made with the agent
adopted, and the conducting liquid which may be a solution of alkaline chlorid,
or a salt having less action on the agent employed. In each compartment a
carbon plate is placed acting as electrode and element.
2nd I place the active paste in two porous cells or vases, each furnished with a
carbon plate, and the two cells are plunged into an external vase containing
the conducting liquid.
3rd I substitute for the preceding porous cells, carbon cylinders filled with
active paste and serving as electrodes which are likewise placed in a liquid
conductor.
4th I use plates of carbon with cavities separated by a cloth, felt, card, or
blotting paper, which are plunged into the liquid conductor. The cavities of
the plates contain the active agent.
5th For a conductor I use a band of paper, tinned, silvered, gilt, coppered,
antimoniated and so forth, on each side of this band are arranged one or more
sheets of blotting paper coated with the active agent, and if desired a sheet of
paper steeped in paraffin. The whole is fixed by bands or by strings forming
a valuable and very economical electrode.
Two of these electrodes form an element, and these two electrodes without the
asulating sheet, which separates them may be united one with the other and
lunged into the liquid separated only by the thickness of the blotting paper. Or
his kind of electrode may be made in spirals round a carbon in form of a column
r of vertical plates, the change of form not affecting the essential conditions herein
eferred to, and which constitute the basis of the invention in relation to the
econdary element, for which the agent may be used to the minimum or maximum,
r in one or other condition only. I frequently place one of the electrodes wound
ound with the matters described in paragraph 5 of letter D, in a porous cell,
ound which the other is rolled. It should be observed that the diaphragm, or the
orous cell can be dispensed with when the agent employed does not offer too
reat a resistance, in this case I plunge the two electrodes into the active paste
aking care that they do not come in contact, and external metallic vases are often
sed lined inside with a thick layer of wax and paraffined resin. The electrodes
re placed in a box or trough which may be of wood coated or lined with wax or

page_text: col-cothar, or it may be of metal similarly lined or of glass or stone. The electrodes
of the consecutive elements may be connected for tension or quantity, and are
formed by charges, discharges and gradual rests. A battery of these elements can
be employed and applied in all cases where accumulators are required, with the
advantage of economy and lightness, some of the elements of the secondary battery
in one or other of the forms indicated connected to a primary battery serves as
regulator to it, whilst in use, and as reserve during rest.
Applications By aid of this method by the employment of a primary battery
seconded if desired by the reserve battery, (in any one of its forms), light may
economically be produced by incandescence or by arc; small motors and machines
employed in small industries may be worked. It is also useful and economical
for continuous alarms, in regulating the currents necessary in galvano plastics,
or electro-metallurgy, in telegraphy, for the telephone, in michrophonics, and
supplying power for locomotion or for industrial purposes.
Having thus described the invention and the method of carrying it into practice.
What is claimed is;
1 The application of the principle as described in paragraphs 9. 10 and 11 to any
industrial purpose.
2nd The construction of the primary element of a zinc and carbon, or zinc and iron
couple, with the special application of the exciting liquid Mn. Cl. Fe³, Cl³.
or Mn, Cl, Fe³, O³, K, Cl, or Mn, Cl, Fe³, Cl³, Na, Cl, to the carbon pole, with
the employment of K, Cl, or Na, Cl, more or less alkalized to the zinc pole
or Fe, Cl. with the iron.
3rd The preparation and application of the exciting liquid Mn, Cl, Fe³, Cl³,
or Mn, Cl, Fe³, Cl³, K, Cl, or Mn, Cl, Fe³, Cl³, K, Cl, or Mn, Cl. Fe³, Cl³, Na, Cl.
4th The reconstitution of this exciting agent.
5th The composition of the vases or cells or diaphragms of minimum resistance,
composed as described of clay, carbonaceous matters and sesqui-oxide of iron.
6th The formation of the secondary element under the various forms indicated, or
conformable with the regulations prescribed by paragraphs 9. 10 and 11, and
in accordance with the details exemplified under letter D.
In witness whereof I the said Arthur Charles Henderson have hereunto set
my hand and seal, this thirty first day of March in the Year of Our Lord One
thousand eight hundred and eighty four.
A
CHENDERSON
(19)