IMPROVEMENTS IN SECONDARY ELECTRIC 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 SECONDARY ELECTRIC BATTERIES communicated to him
from abroad by Nicolas Basset, Electrician 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 17th December 1883.
ARTHUR CHARLES HENDERSON of 47 Museum Street, Oxford Street, in the Parish
of Bloomsbury and county of Middlesex " IMPROVEMENTS IN SECONDARY ELECTRIC
BATTERIES A communication to me from abroad by Nicolas Basset, Electrician
of the city of Paris in the Republic of France
In the formation of a secondary battery on the principles of this invention any
oxyds susceptible of passing from an inferior to a superior state of combination are
employed, as well as any of the chlorides, sulphurets, or phosphurets.
In an economical point of view preference is given to an element composed of
two plates or blocks of retort charcoal or agglomerated carbon, covered with natural
peroxide of iron or granulated colcothar wrapped in blotting paper, and held
together by one or more strings, these plates form the electrodes which are placed
without a diaphragm in a more or less concentrated solution of protochloride of
iron and the whole forms an element of an accumulator or secondary battery.
A number of these elements are coupled for quantity or tension sufficient for
the object desired.
A battery can be formed on the same principle by the use of oxyd of tin,
binoxyd, or deutroxyd of manganese, minium, binoxyd or doutroxyd of copper, in
conjunction with some appropriate conducting liquid. Inert electrodes can be
employed that are not covered with oxyd, and acting simply as conductors which
are placed in an active liquid susceptible of dialysis, such as the protochlorides, the
protosulphates, and the protomanganates, or a mixture of these salts in variable

page_text: proportions, submitted to the action of the current: without excluding any of the
bodies previously mentioned as fulfilling the requisite conditions for effecting the
object.
Secondary action in these batteries or accumulators is in proportion.
1st to the chemical quantity of salt dissolved in the conducting liquid; that is to
say in equivalent proportion to the decomposition, or the reconstitution of this
salt, under the influence of the current.
2nd to the chemical quantity of the oxyd employed; that is to say in equivalent
proportion to the alternate reduction and oxydation of the oxyd.
3rd to the energy, and duration of the charging current produced by the battery,
or by machine
4th to the surface of action: with regard to which an important feature should
be remarked in connection with the conducting liquid, each molecule of which
taken separately represents one of the surfaces used in the mass.
On the other hand when oxyds form at the expense of an equivalent of liquid
it is perfectly clear that these infinitesimal precipitates present collectively
considerable molecular surfaces.
It is for this reason that more concentrated solutions without oxyds to the
electrodes, supply a more energetic and longer lasting secondary reaction than more
diluted solutions, when in both cases the charge by the primary current has been
conducted to the utmost limits.
The choice of external jars rests merely on a point of economy, convenience, and
lightness: any one of the following description may be advantageously employed
viz porcelain, glass, or some inexpensive metal, such as white pig iron, or better
still, wood, compressed paper, or cardboard, taking care, when required to coat the
internal surfaces with a layer of special mastic, which is composed of 30 parts of
yellow wax, 30 parts of resin, 40 parts of paraffin, and 15 parts of pulverized
colcothar, this combination has the property of being an insulator of the first order.

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 16th June
1884.
ARTHUR CHARLES HENDERSON of 47 Museum Street Oxford Street in the Parish
Bloomsbury and county of Middlesex IMPROVEMENTS IN SECONDARY ELECTRIC
TTERIES A communication to me from abroad by Nicolas Basset, Electrician
the city of Paris in the Republic of France
Principles of the invention―
With reference to the technical details of a former patent No 4728 October 4th
1883 for the formation of voltaic couples it should be remarked that the
oxydized chlorureted, and sulphureted compounds there described as susceptible
of passing from an inferior to a superior state of oxydation, chloridation or
sulphuration by the passage of the primary current, can serve as elements in
secondary batteries the discharge current producing inverse effects of equal
importance to those of the primary current.
But circumstances occur in which the conducting liquid plays an important
part due to the value of the primary or secondary reaction.
These effects may be destructive as in the case of the Faure secondary battery
for example where the conducting liquid formed of sulphuric acid dissolves the
litharge resulting from oxydation of the metal plates and forms a quantity of
sulphate of lead which produces disadvantageous local effects and increases
resistance.
Effects of this nature may be observed in many other instances especially
where the liquid conductor is a solution of marine salt, and where a metallic
compound only is used in a superior state of oxydation. Thus when minium
is employed for the electrodes, with a solution of chlorid of sodium as
intermediary it will be observed that the decomposition of the water furnishes
nascent hydrogen and oxygen if the first tends to reduce the peroxyd at one
of the poles, the second is inert at the other. The sodium of the chlorid is
oxydized, and chlorine is liberated which causes great loss in the final result.
This inconvenience can only be remedied by using a conducting solution in
which the body dissolved is in an inferior state of combination so that it can
pass to a superior condition by the effect of the primary current as example
protochlorid of iron acts in this manner, the neutral chromate of soda, or
potash, the neutral manganates, and all the inferior salts capable of passing.
to a superior state. In using protochlorid of iron it will be observed that the
action of the primary current transforms a part of this salt into sesquichlorid
to the detriment of an equal portion which is reduced and passes into a state
of oxydation. In this secondary reaction the protochlorid re-forms and these
alternate reactions are extremely regular. The same is the case with the
neutral alkaline chromates. However peculiar circumstances occur which
are easy to forsee, in which the absorption of the chlorine for instance is
only transitory or incompletely effected. If a solution of protochlorid of
manganese is used for the liquid conductor, this solution passes rapidly into
sesquichlorid, but as this latter body is less stable it easily loses its
elemeuthaloid and liberates chlorine whilst it precipitates oxyd. The same
is the case in all instances where the stability of the super salt formed is
relatively feeble.
In the case of protochlorid of iron as conductor, the reaction caused by the
primary current in presence of the peroxyd of iron to the two electrodes may
be represented by the following symbolical equation 3 Fe Cl + H + 0 =
Fe O+FC+ H. In secondary reaction that is to say the inverse discharge
of the current an effect is produced which can be expressed by the same
equation reversed,

page_text: th With reference to what precedes it should be observed that in secondary
reaction intervening in the liquid conductor a chemical action takes place
determined by the partial de-oxydation of Fe O, the formation of a certain
quantity of water and the chloridation of Fe reduced, which can only be
remedied by the liberation of an equivalent quantity of the secondary current,
so that the conducting liquid itself constitutes a perfect accumulating or
rather polarizing element whose action is added to that of the electrodes.
th The foregoing is so accurate that if two carbon or platinum plates serving as
electrodes are plunged into a solution of protochlorid of iron without any
other addition it can be proved after the passage of the primary current, and 1
the interruption of this current that the closing of the circuit denotes on a
measuring instrument an inverse current of unquestionable energy in
proportion to the chemical quantity of protochlorid decomposed Hence it
results that secondary batteries or accumulators can easily be established
with saline solutions alone provided that they fulfil the conditions above
described
th As a sequence to this main point I have discovered that the duration of the
discharge is sensibly increased when the electrodes whether carbon or platinum
are surrounded by a layer of metallic peroxyd of the same radical as the salts
of the solution this arrangement produces a particular effect by alternations
of reduction and oxydation. The conditions of the solution and the oxyds to
the electrodes is found to be maintained longer and if a secondary battery can
be constructed with oxyds alone to the electrodes in an inert conductor or
with an active conducting liquid alone without oxyd to the electrodes, it is
more advantageous and practical to form a mixed element with oxyds to the
electrodes and an active liquid conductor.
Formation of a secondary battery in accordance with the principles above laid
lown, and as chemically demonstrated whilst reserving the right to employ any
xyd susceptible of passing to an inferior or superior state of combination as well
s the use of any of the chlorids, sulphurets, or phosphurets and so forth dependent
on the general principle of my discovery especially reserving the right to exercise
my choice in the employment of secondary batteries formed of electrodes plunged
nto a dialysable saline solution in accordance with what has already been stated.
I give the preference in an economical point of view to an element composed as
follows: of two plates of retort charcoal or agglomerated carbon covered with
natural peroxyd of iron or granulated colcothar wrapped in blotting paper and
held together by one or more strings, these plates form the electrodes, which are
placed without a diaphragm in a more or less concentrated solution of protochlorid
of iron, and the whole forms an element of an accumulator or secondary battery.
For quantity or tension I couple a number of similar elements sufficient for the
object desired and the secondary battery is at once formed and prepared for
charging.
The drawings accompanying this description accurately show by Figs 1. 2. and 3
battery of elements formed as above described. Fig 1 is an elevation partly in
section. Fig 2 is a plan of the complete battery, and Fig 3 a transverse section of
one of the chambers of the battery. The box a is divided into a certain number
of compartments or chambers 6 communicating with the other at b¹, each
receiving the same number of carbon plates c. c¹ forming exactly similar elements.
These plates if desired are covered with natural peroxyd of iron or granulated
colcothar and then wrapped all over in blotting paper d kept in position by strings.
Figs 4 accurately show one of these carbon plates each of which is supplied with a
binding screw for establishing the communications. These compartments or
chambers contain similar elements composed for example of six carbons c. c¹
plunged into the solution of protochlorid of iron and united two and two as shown.
The elements are connected one with the other to form an accumulating battery
in tension as shown by Fig 2 or for quantity. f. f¹ are the wires of the poles of
the battery. It is perfectly clear that a battery can be formed on the same

page_text: principle by using oxyd of tin, binoxyd or deutoxyd of manganese minium binoxyd
or deutoxyd of copper Cu. O and so forth with some appropriate conducting
liquid in conformity with the rules herein established. I can also employ inert
electrodes not covered with oxyd, acting simply as conductors and placed in an
active liquid susceptible of dialysis such as the protochlorids, protosulphates the
protochromates, and the protomanganates, or a mixture of these salts in variable
proportions, submitted to the action of the current as already described without
excluding any of the bodies previously mentioned as fulfilling the requisite
conditions for effecting my object, whilst expressly reserving to myself the right to
employ them as occasion or circumstances may require. I give no distinct
preference either to the specular or oligist iron, or protochlorid of iron in the shape
of mixed elements, or the simple protochlorid of iron except on account of the low
cost of these products.
Secondary action in my batteries or accumulators is in proportion :-
1st to the chemical quantity of salt dissolved in the conducting liquid, that is to
say in equivalent proportion to the decomposition or the reconstitution of this
salt under the influence of the current.
2nd to the chemical quantity of the oxyd employed, that is to say in equivalent
proportion to the alternate reduction and oxydation of this oxyd.
3rd To the energy and duration of the charging current or primary current
produced by the battery or by machine
4th To the surface of action-With regard to this surface an important feature
should be remarked in connection with the conducting liquid, each molecule of
which taken separately represents one of the surfaces used in the whole mass.
On the other hand when oxyds form at the expense of an equivalent of liquid
it is perfectly clear that these infinitessimal precipitates present collectively
'considerable molecular surfaces.
It is for this reason that more concentrated solutions without oxyds to the
electrodes supply a more energetic and longer lasting secondary reaction than more
diluted solutions, when in both cases the charge by the primary current has been
conducted to the utmost limits.
The choice of the external ja's employed rests merely on a point of economy,
convenience, and lightness porcelain, glass, or some inexpensive metal such as white
pig iron or better still wood, compressed paper, or card board, taking care when
required to coat the internal surfaces with a layer of special mastic.
This mastic is formed of 30 parts of yellow wax, 30 parts of resin, 40 parts of
paraffin and 15 parts of pulverized colcothar, and it has the property of being an
insulator of the first order.
Applications My improved storage, secondary or accumulating battery thus
comprised is therefore formed of two electrodes coated with oxyds, and plunged
either into the conducting liquid which is a saline solution of the same base or in a
simple saline solution conductor. It can be charged by an electrical generator of
some sort or by machine. It has no necessity to be formed and can be charged
immediately it is constructed. The time of charging or of the passage of the
primary current is limited by the reduction of the oxyd of one of the electrodes,
and the reoxydation of the other, by the reduction of an equivalent of the salt
dissolved in the liquid conductor, and the transformation of another equivalent of
super salt or by this latter action alone, when the electrodes are not coated with
oxyd. The result is that the length of the secondary reaction that is to say of the
reflex current is in proportion to the time required for the chemical reconstitution
of the elements disassociated by the primary current. Intensity is in proportion to
the chemical quantity of the oxyd and salt dissolved, or in proportion to this latter
only, to the molecular surfaces resulting from dialysis and to the surfaces of the
conducting electrodes.
The electro motive force is at the mean, 1 volt. I apply this battery for all
purposes and usages of primary batteries, in the production of light by incandescence
orthy are for sunnlving the current for ringing bells or alarms in galvano plastics,

page_text: he telegraph, the telephone, for deflagrating apparatus, the production of motive
ower, for driving machines, locomotives, for traction and propulsion. I also use
he conducting liquid which has been submitted to the dialytical action of the
rimary current as a veritable stock current in the sense that this liquid conveyed
om a long distance occupying a considerable space of time has only to be emptied
to a jar containing an inert electrode and plate of metal of the salt of solution to
nmediately supply a re-established current with all the effects of a veritable
attery This property consequently admits of and facilitates transport of a current
enerator at a trifling cost.
Finally what I claim and desire to secure to myself as my legal right is the
semble as well as the details expressed in this description notably :
The application in the construction of accumulators of the oxyds and haloid
compounds capable of passing to a superior or inferior state of combination
under the action of the voltaic current, and which have been herein before
mentioned.
The discovery and application of the accumulating properties of the dialysable
saline solutions, one portion of which can be reduced whilst the other passes to
the condition of super salt by the primary current, the inverse reaction being
produced under the action of the secondary current.
a The habitual preparation of my accumulator with peroxyd of iron as a coating
to the electrodes with the solution of protochlorid of iron for the conducting
liquid whether this protochlorid is used singly or suitably mixed with proto-
chlorid of manganese or another chlorid capable of liberating chlorine from the
iron salts, or the simple use of the electrodes without the oxyd coating, and
with the same conducting liquid.
The employment of the liquid dialysed by the primary current for conveying
electrical power to a distance
The insulating mastic whose component parts have already been indicated in
conjunction with the use of outer jars of any of the descriptions named.
Finally all the applications herein indicated with others by which electro
motive force can be derived from my accumulators. In other respects I do
not in any way intend to exclude myself from other methods of forming
accumulating batteries with the aid of other oxyds or liquid conductors
resulting from the herein before recited principles and for which I reserve
the exclusive right of employment as circumstances and occasion may require.
In witness whereof I the said Arthur Charles Henderson have hereunto set my
nd and seal this sixteenth day of June in the year of Our Lord' One thousand
ht hundred and eighty four.
Witness
LEWIS. S. PICKERING
Clerk. to A. C. Henderson
A. C. HENDERSON
(L.S.)