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Патент USA US3080454

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March 5, 1963
J. G. E. COHN ETAL
3,080,444
ELECTRIC CELL
Filed June 28, 1960
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INVENTORS
JOHANN c. E. coHN
ANNA P. HAUEL
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ATTORNEYS
March _5, 1963
J. G. E. COHN ETAL L~
3,080,444
ELECTRIC CELL
2 sheets-sheet:
Filed June 28, 1960
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United States Patent
1
3,089,444
"ice
_,
3,080,444
Patented Mar. 5, 1963
2
The apparatus includes a base 12, two upright support
members 14 and 16, and a container 18 which may be
ELEQTRTQ CELL
Johann G. E. Cohn and Anna 1’. Hauel, West Orange,
made of glass. The container 18 is partially ?lled with
NJL, assignors to Engelhard Industries, Inc., Newark,
29, which may suitably be of magnesium or zinc, is
mounted by the support 22 with one end immersed in
the electrolyte within the container 18. A calomel ref
erence electrode 24 is mounted with its ?ber tip immersed
in the electrolyte. It is held in position by a suitable
N.J., a corporation of Delaware
Filed June 28, 1960, Ser. No. 39,289
12 Claims. (Cl. 136-400)
The present invention relates to cells vfor generating
electricity.
As is well known, the standard dry cell includes zinc
as the anode or anodic reactant, and manganese dioxide
as the cathodic reactant or “depolarizer.” The man
a suitable electrolyte as discussed below.
A metal anode
10 clamp 26, which is secured to the upright supporting
member 14.
The cathode assembly includes a central hollow cyl
inder 28, which may be made of glass. The glass cylin
der 28 rests 'on a perforated plastic disc 30, and a di
mixture is pressed around a carbon rod which serves as 15 aphragm (not shown) is inserted between the disc and
ganese dioxide is normally mixed with carbon, and this
the cylinder. This assembly is supported by the bottom
the positive terminal of the dry cell.
of the container 18. Above the disc 30 and within the
in the Leclanché vdry cell described above, electricity
cylinder 28 is a mass of carbon powder 32, with a per
is generated by the anodic oxidation of the metallic zinc
forated carbon disc 34 overlying the powder. An elon
and the cathodic reduction of manganese dioxide. Hy—
droxyl ions are generated concurrently with the cathodic 20 gated carbon rod 36 bears on the upper surface of the
perforated carbon disc 34 and compresses the carbon
reduction of the manganese dioxide. In the electrolyte,
powder 32. The cathodic reactant, hydroxylamine, was
positive ions formed at the anode combine with the hy
added to the electrolyte in the form of hydroxylamine hy
droxyl ions generated at the cathode. When the zinc
drochloride. The hydroxylamine may also be supplied
anode and the cathode are externally connected by an
electric circuit, electrons flow from the zinc to the cath 25 to the cell in pure form or in the form of other salts
or other derivatives of hydroxylamine. It may be either
ode, and thus allow the reaction to» continue.
added to the electrolyte or combined with the carbon
While the Leclanché cell has withstood the test of time,
powder 32. The important thing is to make hydroxyl
and is still widely used, it has several drawbacks for
amine (NHZOH) available at the cathode of the cell.
speci?c purposes. For example, for applications where
weight must be minimized, the manganese dioxide de 30 When it is added to the electrolyte, the hydroxylamine
has access to the carbon powder of the cathode structure
polarizer is relatively heavy per unit of derived current.
Accordingly, important objects of the present inven
through the perforated plastic disc 30 and the diaphragm
mentioned above. The carbon rod 36 is slidably
tion include maintenance of a more constant discharg
mounted within the insulating tube 38. The tube 38 is
ing voltage and reduction of the weight of the cathodic
35 held upright by the brackets 40 and 42, which are
reactant of such cells.
mounted on the vertical supporting post 16. The cylin
These objects are achieved, in accordance with the
der 23 is closed by the apertured stopper 44 through
present invention by the use of hydroxylamine as the
which the carbon rod 36 passes. A weight 56, which, in
cathodic reactant or depolarizer in an electricity gen
the present case, weighed 2.5 kilograms, is mounted on
erating cell. Cells employing this cathodic reactant have
the upper end of the carbon rod 36 to compress the car
a relatively constant discharging voltage. In addition,
bcn powder into a conductive mass.
hydroxylamine is a relatively light weight cathodic re
The circuit- for the apparatus of FIG. 1 is shown in
actant; thus, manganese dioxide weighs several times as
FIG.
2. In FIG. 2 the electrolytic cell is shown only
much as hydroxyllarnine, for an equivalent amount of
schematically. Thus, the apparatus includes the con
cathodic reactant.
tainer 18', the anode 20’, the calornel reference electrode
Other objects, features and advantages of the inven
24’, and the cathode assembly 36’. The potentiometer
tion may be readily apprehended from a consideration
52 is connected between the cathode assembly 36' and
of the following detailed description and from the draw
the reference electrode 24'.
ings, in which:
A double-pole, double-throw switch 54 is connected be~
FIG. 1 shows a cell employed for electric cell test
tween the anode 20' and the cathode assembly 36’. A
ing purposes;
milliammeter 56 is connected in series with the anode 20',
FIG. 2 represents circuitry employed with the appara
between the anode and the switch 54. By means of the
tus of FIG. 1; and
switch 54, the anode to cathode circuit may be connected
FIG. 3 is a plot showing cathode potential versus time
during a discharge at a constant current rate for various 55 either to a suitable load, as represented by resistor 57, or
to a circuit including variable resistor 58 and the source
electric cells.
of direct current 60, which are employed in establishing
With reference to FIG. 1 of the drawings, an arrange
suitable test conditions.
ment is shown which conveniently permits the testing and
As mentioned above, in the testing of cathodic reactants,
comparison of cathodic reactants. It is a primary cell
including a cathode assembly as described below. In 60 it is customary to isolate the cathodic structure from the
action taking place at the anode. In addition, current
the present case cathode potentials may be studied inde
is preferably passed through the cell at a constant rate.
pendently of anodic conditions by the use of a standard
In connection with the present examples, a constant cur
reference electrode. The apparatus is similar to that
rent flow of 15 millamperes is maintained by connecting
which has been used by others for electric cell experi
the source of direct current 60 and the variable resistance
ments, see Journal of the Electrochemical Society, vol
58 into the anode-to-cathode circuit, and adjusting the
urne 103, pages 94 and 95, C. K. Morehonse and R.
resistance
58.
Glicksman, 1956.
3,080A44
4
"'Amum'b‘er rofterts1'‘eriipldying hydroxylamine as the
dioxide as cathodic depolarizers under fuel cell condi
tions. 'The Lelanché cell ‘normally operates asa primary
cell with an electrolyte having a pH of 5 to 7. Under
cathodic reactant were performed with the apparatus
shown in FIG. 1. In each case, the minutes of operation
were counted from a closing of the 15 milliampere circuit.
these conditions the voltage decline rate, although quite
The test conditions for four examples are given in the 5 high, is not considered excessive. However, the MnOz
following Table I:
depolarizer used in the Lelanché cell is not satisfactory for
Table I
‘ _
Cell A
Cell 13
Cell 0
Cell D
?'ébolhiiéer ______________ __'.___ 3gms. NHiOH ______ ._ none ________________ ._ 3 gms. NHzOI-I ..... -_‘. "none.
Cathode:
'
‘
Alkyd?»-
~
carbon ______ __‘ ______ .4
-
‘Zine
Electroly
‘
,
v
---- -_
carbon ______________ __
Vim‘
6O ‘ccnoianaqueous
--
solution containing
V~perliten200 gms.‘ of,
.
_
v
‘carbon.
Me
solution containing
?r liter‘250 g'ms.
‘
the depolarizer;
.,
g?l‘zBHeO;
‘ saturated with
saturated with
_
,.
‘ 130cc; of an aqueous
IgBI‘QGHzO and
' NHiOl.
depolarizer.
.
.
solution containing
per liter 250 guts. of
‘211012.250 gins. of
'
on ______ ._
' 60 cc. of an aqueous,
solution contain‘ln g
‘per liten200 gms. of
Zn'Glz; 250 gms. of '
fNHtCl‘and the
car
_
60 cc. oi'an aqueous
Mg(OH)g.
Mg(OH);.
OperatingI'I‘emp;__'_'-_ ....... __'_ ‘28° C;
28° 0;.‘ ______________ _.
28° C.
ConstantCurrent Rate,
l5 ................... _.
15.
15 ____ __
'Milli‘amps.
n1 measles ‘A ‘ape C,'_t_h'e weight ‘at 'hydroxylainirie‘ is
the. Weight 'Qf. hyqrdrylamilis.finslvde'd ‘in. the h'y'drox'y'l
amine hydrochloride which was v‘added to "the ‘electrolyte,
asvmentioned" aboveuThe' electrolyte for Example A was
use with_,_an alkaline electrolyte and is therefore not suit
able for fuel cells which=generally require alkaline electro~
lytes-
._
.,
.
.
.
i
25
The superiority of the hydroxylamine depolarizer of this
invention to a MIlOg‘ClCPOlZlI'lZGI‘ in the presence of an
jIn‘?the reactions of ‘Examples’ A and'C set forth above,
themetal is oxidized ‘theihy'droxylamine is reduced.
Energy“ producedtb'y these reactions is available as elec 30
parison of cell C, which shows a low decline rate in FIG.
slightlyua‘cid vabout ‘(pH '5) and‘that ‘forAExaniple' C‘W'as
basic abeiitlpli 815).’-..
. .
a.
.
H
-
.
v
.
tricityviin much the: s'amq'ennner as in the case of the
Lecleljlshé @811 slessribédebofve I .
.
.
..
.
alkaline electrolyte maybe appreciated through acom
3 inthe presence of an electrolyte at a pH of 8.5, with a
Mn02 depolarizer at the same pH. The latterdepolarizer
was tested in a cell with'a carbon cathode, ‘a ‘magnesium
anode andna magnesium bromide electrolyte. It was
.
, \‘Iq‘able?Ill shows the cathode potential forthe test condi
found to drop from a cathodic potential of +0.3 volt'one
tions' described in Table “Examples Band n'were con
trolnerraniplesand involvedfte's'ts ‘in whichino depolariier,
houriafgter placing the cellnin circuit to ~07 ‘volt after a
41/2 hour period.’ In contrast, cell C had a cathodic po
tential-Vafter, one hour of O'volt and after 41/2 hours of
i.e. cathodic reactant, ‘was' employed:
—'_Q.1 volt. Thus, hydroXylam-ine is clearly superior‘to
electrolyte conditions normally employed in fuel'cells.
‘Table II
manganese dioxide as a depolarizer ‘under the alkaline
'
*caasae' Potential (vans)
Minutes
Cumulative
>-
Cell A ‘
i
"
-
Cell B
, . -.-0.145
-~
-
~
-
<
Cell D
_+0._086
-0. 236
---.
'
Cell 0
40 no _It isto be understood that the above-described arrange
mentsareillustrative of the application of the'principles
of the invention.__ ‘Numerous other arrangements may be
devised by those skilled in the art'rwithout departing from
-—0.325
‘+0.003
—0. 541
,—-0.031
_—0.703
~01 041
—0. 061
-—0. 811
—'0.898
-—O. 0?.0
, 70.939
'.
40.939
the spirit and scope‘oi the invention.
45
What is claimed is:
‘ l.
o
o
_
I
electricity generating cell'comprisin‘g an anode
madev of_a metal selected from the ‘group consisting of
zinc and magnesium, a‘ cathode'including carbon, anelcc
trolytenin contact wanton said anodeand said cathode,
The plots of FIG.‘3, show the'cathode ‘potentials for 50 and NHzOl-lidiss'ol'ved‘in said’ electrolyte.
I
the ‘test ‘con'ditionsjof ‘Table 11in‘ graphical'form. The
2._ “In combinationpanodic andicathodic ‘terminals, an
electrolyte, means including a conductiveanodic structure
in electrical contact with/said'anodic'teiminal ‘for supply
ing positively charged ions to said electrol'yte,'and means
designatedA ‘and "C indicate the'cathode potential with
hydroxylamine ‘present ‘in the cell, with an acid ‘and _,_an 55 including a conductive structure‘in ‘contact'with said’ca
letter designations‘of thejplots- correspond to theicell'desig
nations ‘of Table L and :Table II;"accordingly,' the curves
alkaline electrolyte,"respectively. , Curve D shows ‘the
tliodic ‘tastiest and said'e'lec'trolytefor reducing said posi
cathode potential when no hydroxylamine was presentin
tively'ch'arged ions and‘n'eutraliz'ing’their' charge, said last
the cell, and with'anialkaline electrolyte corresponding to
mentioned means also comprising NHzOH.
'3. Inca process for generating‘electricity, the step of
vIn the customary manner, ‘the’ potentialis expressed'in 60 adding a cathodic reactant selected from the group con
sisting of NH2OH"‘and"salts' meteoric ‘an electric cell
volts'iwhich represent‘the» potential di?er'ence between the
including an electrolyte and anodic means for supplying
cathode and‘ a_ reference hydrogen, ‘electrode.’ Acutal
positivelycharg‘ed ions to said electrolyte.
measurements were ‘takenkbetween the ‘cathode and ,a
“4. ‘An 'electricity'generating cell comprising an anode, a
commercial'calomel reference'electrode, and the calomel
that of test condition C.
.
.
.
,
,
readings were ‘then converted to‘ standard “hydrogen-po 65 cathode structure including carbon, and an electrolyte in
contact with both said anode and said cathode structure,
.
.
tentials.”
' ‘In addition to‘ the use of hydroxylamine-‘as the cathodic
saidv electrolyte including NHZOH.
reactant ‘in. a celliasdescribed, it may, also, be employed
5. An'electricity generating cell comprising an anode, a
in‘a‘ fuelcell. ' 'In this case, the hydroxylamine is fed into
cathode/structure, an'electrolyte‘in contact with both said
the‘ cathodic section of the fuelmcell and is again employed 70 anode and ‘said cathode structure, and means for’ supply
as'an' oxidizing agent to oxidize the anodic reactant which
ing NHZOH to said cathode structure.
would also be supplied to the anode of the fuel cell.
' 6. A rnethojdlfor operating an electrical cell comprising
._With regard to, advantages of hydroxylamine, as a de~
supplying NHZOH to the cathodic structure of the cell.
polarizer, itsrelatively light weight has beennoted above.v
_ 7.‘_An electricity generating cell comprising an anode, a
'It is also useful to compare hydroxylamine and‘ manganese 75 cathode structure, and an electrolyte in contact with both
aeedaee
5
said anode and said cathode structure, said electrolyte
including dissolved NHQOH and magnesium bromide.
8. An electricity generating cell comprising an anode, a
cathode structure, and an electrolyte in contact with both
said anode and said cathode structure, said electrolyte
including dissolved NHZOH and zinc chloride.
9. In a process for generating electricity, the step of
adding a cathodic reactant selected from the group con
sisting of NI-I2OH and inorganic salts thereof to an elec
tric cell including an electrolyte and anodic means for 1°
supplying positively charged ions to said electrolyte.
10. A depolarizer for an electric cell comprising carbon
6
with both said anode and said cathode structure, said elec
trolyte including dissolved NHZOH.
12. An electricity generating cell comprising an anode,
a cathode structure, and an electrolyte in contact with both
said anode and said cathode structure, said electrolyte
including dissolved NHZOH.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,589,635
2,874,079
2,880,122
OTHER REFERENCES
mixed with a cathodic reactant selected from the group
consisting of NH2OH and inorganic salts thereof,
11. An electricity generating cell comprising an anode,
a cathode structure, and an alkaline electrolyte in contact
Smith et al ____________ __ Mar. 18, 1952
Lozier _______________ __ Feb. 17, 1959
Morehouse et al _______ __ Mar. 31, 1959
Creighton: Electrochemistry Principles, volume 1, 1924,
page 270.
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