Improvements in the Accumulation of Electrical Energy and Apparatus therefor.
Year: 1889

page_text: Date of Application, 7th June, 1889
Complete Specification Left, 24th Dec., 1889-Accepted, 25th Jan., 1830
PROVISIONAL SPECIFICATION.
Improvements in the Accumulation of Electrical Energy and
Apparatus therefor.
I, FRIEDRICH MARX, of 91, Grossbeerenstrasse, Berlin, in the Empire of Germany,
Chemist, do hereby declare the nature of this invention to be as follows:-
My invention relates to the accumulation of electrical energy and to apparatus
therefor.
In apparatus as hitherto generally used for accumulating electrical energy through.
the medium of chemical changes, a change occurs in the electrodes when charging
the apparatus and a further change takes place in the electrodes when discharging the
apparatus. These changes in the electrodes are objectionable especially when the
discharge cannot be effected at the place where the apparatus is charged.
According to iny invention I accumulate electrical energy in a liquid by using an
apparatus in which the liquid is chemically changed through the action of an electric
current; the accumulated energy in the said liquid being discharged by setting free
the electric current in another apparatus.
For charging I employ a glass vessel, in which I introduce a suitable metal such
as iron or a solution of a metallic salt such as protochloride of iron with an addition
of an acid such as hydrochloric acid. Any metal or metallic salt can be employed,
which in the presence of an equivalent quantity of acid will become oxidized when
submitted to the action of an electric current the protochloride of iron, for example,
being changed into perchloride of iron. When the salt is dissolved I place in the
liquid two electrodes made of a suitable conducting non-metallic material such as
carbon which will not be acted upon by the salt, one of which plates is connected to
the positive pole and the other to the negative pole of an electric machine, by which
the liquid is submitted to the action of an electric current.
The liquid thus charged with electricity I propose to call "Electrolin."
It is perhaps more advantageous to use three electrodes that is to say, a negative
between two positive electrodes.
In order to discharge an accumulator made in this manner, it is necessary to use
electrodes of a different kind from those used for charging it, that is to say, one of
the electrodes must be formed of some kind of metal and the other of a conducting
non-metallic material such as carbon which will resist the action of the salt. Directly
the electrodes are connected up, a powerful electric current is produced and the liquid
is gradually decomposed.
COMPLETE SPECIFICATION.
Improvements in the Accumulation of Electrical Energy and
Apparatus therefor.
1, FRIEDRICH MARX, of 91, Grossbeerenstrasse, Berlin, in the Empire of Germany,
Chemist, 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 :-
My invention relates to the accumulation of electrical energy and to apparatus
therefor.
In apparatus as hitherto generally used for accumulating electrical energy through.
the medium of chemical changes, a change occurs in the electrodes when charging -
./7

page_text: the apparatus and a further change takes place in the electrodes when discharging the
apparatus. These changes in the electrodes are objectionable especially when the
discharge cannot be effected at the place where the apparatus is charged.
According to my invention 1 accumulate electrical energy in a liquid by using an
apparatus in which the liquid is chemically changed through the action of an electric
current, protochloride of iron for example being changed into perchloride of iron;
the accumulated energy in the said liquid being discharged by setting free the electric
current in another apparatus.
The liquid charged to a certain extent with electrical energy I propose to call
"Electrolin."
Any metal or salt of metal, which in the presence of an equivalent quantity of acid
will become oxidised or changed into a salt corresponding to a higher oxide of the
said metal through the influence of the electric current, can be used in preparing the
Electrolin.
The electrodes of the charging apparatus are made of a suitable conducting
material which will not be acted upon by the salt such for instance as carbon and one
of the electrodes of the discharging apparatus is made of a conducting material
which will resist the action of the salt and the other electrode is made of some kind
of metal.
The method of preparing and using electrolin will be well understood by the
following description which is given as an example, reference being had to the
accompanying drawing the two figures of which represent sections of accumulators
or storage batteries made according to my invention.
A glass vessel is filled with about 450 grammes of protochloride of iron,
900 grammes of water and 500 grammes of hydrochloric acid (of 25 per cent.
H. CI).
After the salt is dissolved two carbon plates are placed in the vessel
without touching one another. One of the plates is connected to the positive and
the other to the negative pole of an electric machine.
It is perhaps more advantageous however to use three electrodes as shown in
Figure 1 of the drawing so as to have the negative electrode 6 between two
positive electrodes a, a. When passing an electric current through, a decomposition
of the liquid occurs at once, the solution which is at first of a grass-green colour
becoming, whilst producing hydrogen at the negative electrode, of a greenish-yellow,
then dark yellow and finally a yellowish-brown colour. If one of the plates is
taken out while the electric current is in action and is placed near the surface of
the liquid large sparks will pass between the wet plate and the liquid. When the
liquid ceases to receive further electric energy the negative plate first and then the
positive plate must be taken out of the liquid after previously moving them several
times to and fro. The electric current has now converted the liquid into electrolin
(2 Fe Cl, 2 H Cl = Fe, Cl + H₂).
When charging, the hydrogen will be seen to rise at the negative electrode while the
liquid converted into electrolin will be seen to sink down at the positive electrode. A
circulation is consequently caused in the apparatus in the direction indicated by the
arrows in Figure 1. The liquid prepared in the manner described forms electrolin.
The electrolin in the present case consists mainly of perchloride of iron in a watery
solution formed through the electric current; the solution could however instead be
concentrated by evaporation or by means of water-absorbing bodies, such as lime,
sulphuric acid, chloride of calcium, &c., and finally be crystallised if care be taken
that the solution is neither exposed to direct sunlight nor to dust nor brought into
contact with metals. The electrolin is either used concentrated or diluted with water
for producing the electric current.
In accumulators as heretofore constructed the same electrodes were used for
charging and discharging but in my accumulator the electricity from the electrolin
cannot be set free by the same electrodes as those used in charging. This can only
be effected by using an electrode formed of some kind of metal and an electrode of
a conducting material which will resist the action of the salt such for instance as a
carbon plate.

page_text: The carbon plate K which must be highly porous or have numerous perforations
should fill the greatest part of the jar say three fourths or four fifths and be placed
between two metal plates e, e¹ which are preferably made of iron as shown in Figure 2.
The moment the plates are connected up a very strong electric current is produced
and the liquid is gradually decomposed and finally becomes again grass-green.
Towards the end of the discharge hydrochloric acid will be found as well as proto-
chloride of iron and a small portion of oxygen combined with the iron deposits
oxygen on the metal plates while the greatest part of the freed oxygen escapes. The
process may be illustrated by the following formula Fe, Cl + H, O=2 Fe
Cl, 2 HCl + 0.
Experiments have proved that even with long continued use the metal plates do
not decrease in weight but on the contrary I find that in the discharging apparatus
when the current is not connected up metallic iron is deposited on the metal electrodes.
It is therefore advisable to take the metallic electrodes out of the liquid when the
apparatus is not in use.
The electrolin containing the perchloride of iron acts quite differently to ordinary
perchloride of iron. Two electrodes, namely, one of carbon and the other of metal
when placed in an ordinary liquid with perchloride of iron and connected up will
produce an electric current but the metal plate will very soon be dissolved. On the
contrary, when using electrolin made with perchloride of iron, the metal electrodes are
not attacked at all.
Instead of using ready made protochloride of iron for preparing electrolin on a
large scale the metal itself can be introduced. For example, 100 parts by weight of
iron turnings are put into the decomposing vessel of the charging apparatus together
with 750 parts by weight of hydrochloric acid (25 per cent. H (1) which is dissolved
through the influence of the electric current. At first the iron dissolves easily when
hydrogen is freed but only protochloride of iron is then formed. The electric current
accelerates the formation of protochloride of iron and afterwards changes the proto-
chloride thereby forming perchloride of iron.
Electrolin is therefore produced when a metal or salt of a metal in the presence
of an equivalent quantity of acid is oxidised or transformed through the influence of
an electric current.
Other metals which usually demand stronger chemical agents to cause their
oxidation act in a manner similar to iron.
The electric current replacing the strongest chemical agents causes with the same
chemical combination of the metallic salts an easier decomposition, as regards
reduction under delivery, of the generating or oxidating current; electrolin consists
of any metallic salt solution produced by the aid of an electric current.
Experiments made with copper which is not readily soluble in hydrochloric acid
as well as those made with antimony and tin have yielded equally good results.
The most suitable acid for producing electrolin is hydrochloric acid as it enables
even an ordinary practical man to ascertain the termination of the charging process
by the smell of chlorine. Nevertheless other acids can be used; for instance, electrolin
can be produced by the action of an electric current upon ferrous sulphate in a con-
centrated watery solution to which sulphuric acid is added. The solution changes
colour from green to a brownish-yellow and freeing hydrogen, thus forins a sulphuric
solution of ferric oxide (2 Fe SO, + H₂ SO₁ = Fе, (SO4)3 + H₂) which is electrolin.
It is evident that in choosing a metallic salt for the preparation of electrolin the
acid to be used must be that which forms the base of the metallic salt.
From the above it will be understood that the process herein described is entirely
different from the ordinary method of accumulating electricity in existing accumulators
n which, when connected up, an electric current is at once generated. This is not
the case in an electrolin charging apparatus as it is necessary to have one of the
electrodes replaced by a metal plate or rather to have a special discharging apparatus
o recover the accumulated electric energy. Moreover there is no appreciable altera-
ion in the electrodes, either during the charging or discharging, no risk of the plates

page_text: bending or twisting and consequently all inconveniences arising therefrom are removed.
The chemical alterations in the present process occur only in the liquid itself.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed I declare that what I
claim is
(1.) The herein described process of accumulating electrical energy in which metals
or solutions of metallic salts with an addition of their equivalent acid are for the
purpose of oxidation submitted to the action of an electric current and in which
electrodes are used made of a conducting non-metallic substance which will resist the
action of the salt.
(2.) The herein described process of generating an electric current from a watery
metallic salt solution prepared by the process referred to in claim 1, by the use of an
electrode made of a conducting, non-metallic substance which will resist the action of
the salt and a metal electrode.
(3.) The use of a metallic salt either in a liquid or a solid form charged with
electrical energy and prepared in the manner indicated in claim 1 by oxidation or
transformation produced by means of an electric current substantially as hereinbefore
described..
1000
G. F. REDFERN & Co.,
4, South Street, Finsbury, London, Agents for the Applicant.