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Патент USA US3057777

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Get. 9, 1962
J. s. DERESKA ET AL
3,057,760
POLYHALOGEN DEPOLARIZERS
Filed July 5, 1960
~
3 Sheets-Sheet l
4
9
6
2
l
2'0
DISCHARGE CONTINUOUSLY
AT A CURRENT DRAIN OF 200ma.
Zn/(CH3)4 NI 04
4.5
Zn/ (Mn 02)
4.0 —
/
3.3 AME-MIN.
PER Gm. Mn 02
|4.s AMPS-MIN. PER
Gm. POLYHALIDE
0.5 -
X.
o
I
|
I
0
|
|
l
I
i
l
l
I
|
4o
5
DISCHARGE TIME (HRS.)
INVZ'NTORS
JOSEPH S. DERESKA
7,4"
j
JAMES O-KOEHLER
ALBER T
'
BY
F.Vl AL
7?. MAM
ATTORNEY
Oct. 9, 1962
J. 5. DERESKA ET AL-
3,057,760
POLYHALOGEN DEPOLARIZERS
Filed July 5, 1960
3 Sheets-Sheet 2
2'0
DISCHARGED CONTINUOUSLY
ATA CURRENT DRAIN OF 560ma.
45
Zn/(CH3)4NICI4 (1/2 D SIZE CELL)
(VCOILRTAUSGIE)D
0.5
001
2/194
|
|
lsgol
|
I
lwlool
I
DISCHARGE TIME (MIN.)
2.0
OJOHM
ZH/CIZG.)
Zn/F'grIBrCI2
4.5 —
zn/Agz o2 (2-)
E
\
g‘:5 Lo_*Zn/MOQ)
HgO/Zn
<
'3
O
>
Zn/MnO2
0.5
ollllllllllllll
5
SERVICE LIFE (MIN)
2"" 5.
1o
uvvnvroes
JOSEPH
$.DERESKA
JAMES o. KOEHLER
ALBERT F. v NAL
71
M.
A 7' TORNEV
Oct 9, 1962
J. 5. DERESKA ET AL
3,057,760
POLYHALOGEN DEPOLARIZERS
Filed July 5. 1960
3 Sheets-Sheet 3
m
0
F
V
N
O
_
h
mI0JAl2UF‘|wv’d>Y-mUu
UONZIU
_
.
_
_
_
m
V
N
O
_
uvvmrms
JOSEPH s. DERESKA
JAMES o. KOEHLER
ALBERT F. VINAL
By
?W
%TTORNEY
3,057,760
United States Patent 0
2
1
ing of an organic or inorganic electron donor containing
a point of high electron density such as an amine, metal
ammonium complex, metal-amine complex, sul?de or
phosphine and a polyhalogen electron acceptor.
3,057,760
POLYHALOGEN DEPOLARIZERS
Joseph S. Dereska, Parma, James O. Koehler, Parma
Heights, and Albert F. Vinal, Shaker Heights, Ohio,
assignors to Union Carbide Corporation, a corporation
The following are representative compounds compre
hended by the above de?nitions.
of New York
Filed July 5, 1960, Ser. No. 40,886
14 Claims. (Cl..136——137)
A. Inorganic polyhalides:
Potassium dichloriodide
Potassium tetrachloriodide
This invention relates to polyhalogen depolarizers for
use in galvanic cell systems.
Patented Oct. 9, 1962
Cesium triiodide
Cesium dichloriodide
Cesium tetrachloriodide
Cesium tribromide
Cesium diiodochloride
Cesium diiodobromide
10
Galvanic cells conventionally comprise a consumable
anode, a separator, an electrolyte and a cathode depolar
izer. Those cells which do not have e?iciently reversible
chemical reactions are termed primary cells. Where such
cells are assembled without one of the essential com 15
Cesium pentaiodide
Cesium heptaiodide
ponents, such as the electrolyte, they are called deferred
action cells. Cell systems which, after discharge, can be
restored to essentially their original electrochemical state
are termed rechargeable cells.
Heretofore most of the depolarizers used in the systems 20
above mentioned have consisted of solid, metal oxides
Cesium nonaiodide
Cesium dibromoiodide
Cesium dichlorobromide
Rubidium triiodide
Rubidium dichloriodide
such as manganese dioxide, mercuric oxide and silver
Rubidium tetrachloriodide
oxide. Such compounds have excellent depolarizing char
Rubidium dichlorobromide
acteristics, but possess de?nite limitations as regards their
Rubidium dibromochloride
potential levels, service capacities and other discharge 25
Rubidium diiodochloride
characteristics. In this respect, it should be remembered
Rubidium iodobromochloride
that increasing technological advances are making greater
B. Alkyl ammonium compounds:
performance demands on batteries, which demands appear
(a) Triiodides (I3—)to lie beyond the scope of cell systems employing metal
oxide depolarizers. Therefore, a need exists for new de 30
polarizers which can extend performance beyond the
limitations of the metal oxides. Further, certain mate
rials from which metal oxide ‘depolarizers are prepared,
such as manganese ores, are not always available in large
quantity from local sources and must be imported. Tedi 35
ous processing techniques are required to convert such
ores to the active depolarizer form.
Accordingly, the main object of this invention is to pro
vide novel polyhalogen depolarizers which will permit
efficient operation at high current drains and at high volt~ 40
age levels.
(f) Dichlorobromide (Bray);
Tetraethylammonium
Tetrapropylammonium
be readily obtained from local sources using comparative
ly simple processing techniques.
In the drawings:
FIG. 1 is a sectional, elevational view of a cell employ
ing the subject depolarizers;
FIG. 2 is a perspective view of a unit cell for a flat
cell construction.
FIG. 3 is a graph illustrating the continuous discharge 55
characteristics at 200 ma. of cells using certain depolar
izers of the invention;
FIG. 4 is a graph illustrating the continuous discharge
characteristics at 560 ma. of cells using certain depolar
60
izers of the invention;
FIG. 5 is a graph comparing the service life of cells
using various depolarizers; and
Tetrabutylamrnonium
Trimethylammonium
Dimethylammoniu'ni
Methylammonium
Isopropylammonium
t-Butylammoniurn
Tri-n-propylammonium
Di-n-butylammonium
(g) Dichloroiodide (IClfF
Methylammonium
Dimethylammonium
Trimethylammoniuin
Tetramethylamm'onium
Ethylammonium
Diethylammonium
Tetraethylammonium
65
Tetra-n-propylammonium
70
lsopropylammonium
t-Butylammonium
Tetra-n-butylammonium
n-Amylammonium
n-Decylammonium
The polyhalogen compounds subject of the present in
polyhalide anion containing an odd number of halogen
atoms. “P'olyhalide" complexes are compounds consist
(e) Tribromides (Br3‘)'—-'
Tetramethylamrnonium
proved electrochemical system for galvanic cells utilizing
organic or inorganic polyhalogen depolarizers which can
least equal to that of potassium, and a homo- or hetero
(d) Nonaiodides (I9‘)—Tet'rame'thylarnmonium
Tetrabutylammonium V
A further object of this invention is to provide an im 45
vention are polyhalide salts and polyhalide complexes.
By “polyhalide” salts are meant compounds consisting of
an organic or inorganic cation having an atomic radius at
Tetrapropyla'rnmoniuin
Tetrapropylammonium
Tetrabutylammonium
(c) Heptaiodides (I7-)—'
Tetraethylammonium
inorganic polyhalide depolarizer.
vention.
(b) Pentaiodides (I5)—
Tetramethylammonium
Tetrarnethylammonium
Another object of this invention is to provide an im
proved electrochemical system employing an organic or
FIG. 6 is a graph the curves of which show the per
tormance of a rechargeable cell in accord with the con
Tetramethylammonium
Tetraethylammo'nium
Tetrapropylammonium
Tetrabutylammonium
(h) Dibromoiodide (IBr2—)—
Methylammonium
I
3
3,057,760
4
Dimethylammonium
Tetramethylammonium
Melamine
Morpholine
2,5-diaminopyridine
Pyrrolidine
Tetraethylammonium
Tetra-n-propylammonium
Tetra-n-butylamrnonium
Di-n-propylammonium
Tri-n-propylammonium
Pyrrol
Piperidine
Quinoline
N-methylpyridine
Tri-n-butylammonium
s-Butylammonium
(i) Tetrachloroiodides (ICl4-)—
Pyridine
10
Methylammonium
Dimethylammonium
a-Picoline
y-Picoline
Trimethylammonium
Tetramethylammonium
Collidine
Ethylammonium
Diethylammonium
Triethylammonium
Tetraethylammonium
n-Propylammonium
Tripropylammonium
20
Tetra-n-propylammonium
Isopropylammonium
Diisopropylammonium
Tetra-n-butylammonium
n-Butylammonium
s-Butylammonium
n-Amylammonium
n-Decylammonium
25
Tetrabutylammonium
(k) Diiodochlorides (I2C1-)—
Tetramethylammonium
Tetraethylammonium
a-Picoline
Collidine
30
35
Tetra-n-propylammonium
Tetra-n-butylammonium
(I) Tetraiodochloride (I4Cl-)-—
Tetramethylammonium
(m) Chlorobromoiodides (IBrCl-)—
Tetramethylammonium
Tetrapropylammonium
Dimethylammonium
Trimethylammonium
Tetra~n~butylamm0nium
40
a-Picoline
45
Tetramethylammonium '
(d) Dichloroiodide-—
Melamine
Morpholine
2,5-diaminopyridine
Propylenediamine
Triethylene tetramine
55
60
Z-methyl-S-ethylpyridine
Collidine
65
8-methylquinoline
6-nitroquinoline
2-chloroquinoline
Quinaldine
Triethylene tetramine
Caffeine
Tetraethylene pentamine
(e) Dibromoiodide (IBr2-)—
Ethylenediamine
Propyldiamine
Quinine
(e) DibromoiodideMorpholine
Pyrrolidine
1,3-diaminopropane
D. Heterocyclic amines:
(a) Triiodides (13")
Pyrrolidine
Pyrrol
Piperidine
Quinoline
N-methylpyridine
Pyridine
a-Picoline
'y-Picoline
Triethylene tetramine
Propylenediamine
1,3 diaminopropane
Collidine
8-methylquinoline
G-nitroquinoline
2-chl0r0quin0line
Quinaldine
C. Polyamines:
(a) Triiodides (Ia-)
Ethylenediamine
(d) Dichloroiodide (ICl2_)—
Ethylenediamine
6-nitroquino1ine
2-chloroquinoline
Quinaldine
(C) Dichlorobromides (BrCl2-)—
Melamine
Morpholine
2,5-diaminopyn'dine
Pyrrolidine
Pyrrol
Piperidine
Quinoline
N-methylpyridine
Pyridine
Z-methyl-S -ethy1-pyridine
'y-Picoline
Isopropylammonium
Dibromochlorides (Br2Cl-)-—
(b) Tribrornides (Br3-)—
Ethylenediamine
Triethylene t'etramine
(c) Dichlorobromides (BrC12-)—
Ethylenediamine
Propylenediamine
1,3 diaminopropane
Tetraethylene pentamine
S-methylquinoline
6-nitroquinoline
2-chloroquinoline
6-chloroquino1ine
Quinaldine
(b) Tribrornides (Br3_)—
Morpholine
Pyrrolidine
Piperidine
Quinoline
8-methy1quinoline
N-methylpyridine
'y-Picoline
(j) Diiodobromides (I2Br')
Tetramethylammonium
Tetraethylammonium
Tetrapropylammonium
Z-methyl-S-ethylpyridine
75
Pyrrol
Piperidine
Quinoline
3,057,760
N-methylpyridine
Pyridine
a-Picoline
'y-PiCOIiIIC
5
Benzyl amine
Dibenzylamine
Tribenzylamine
Urea
Guanidine
Collidine
(d) Dichloroiodide (ICl2")-—
S-methylquinoline
Benzylamine
Dibenzylamine
Tribenzylamine
6-nitroquinoline
2-chloroquinoline
Quinaldine
(f) Tetrachloroiodide (1014-)
Urea
10
Guanidine
Melamine
(e) Dibromoiodide (IBr2-)—
Morpholine
Urea
2,5-diaminopyridine
Pyrrolidine
Pyrrol
Piperidine
Piperazine
Quinoline
Namethylplyridine
2-methyl-5-ethylpyridine
Guanidine
Tribenzylamine
(f) Tetrachloroiodide (ICl4-)——
15
Urea
Guanidine
Benzylamine
Dibenzylamine
Tribenzylamine
(g) Diiodobromide (I2Br“)—Tribenzy1amine
(h) Diiodochloride (I2Cl-)—-Tribenzylamine
(i) Chlorobromoiodide (IBrC1-)‘-’—
Benzylamine
Dibenzylamine
Tribenzylamine
20
a-Picoline
'y-Picoline
Collidine
S-methylquinoline
6-nitroquinoline
2-chloroquinoline
Quinaldine
Urea
Ca?'Teine
Quinine
(g) Diiodobromide (I2Br-)Pyridine
Quinoline
Morpholine
Piperidine
Piperazine
Guanidine
(j) Dibrornochloride (Br2Cl-)--Tribenzylamine
30
F. Phosphorus and sulfur compounds:
Trimethyl sulfonium dichloroiodide (CH3)3SICl2
Trimethyl sulfonium tetrachloroiodide (CH3)3SICI4
35
u-Picoline
S-methylquinoline
(h) Diiodochloride (1201-)
Pyridine
Quinoline
Morpholine
Piperidine
40
Tetramethyl phosphonium dichloroiodide
P‘iperazine
a-Picoline
S-methylquinoline
45
(i) Chlorobromoiodide (IBrC1)—
Morpholine
Pyrrolidine
Pyrrol
Piperidine
Quinoline
N-methylpyridine
50
Pyridine
or-Picoline
'y-PiCOllDG
(j) Dibromochloride (Br2C1-')-—
Pyridine
As shown in FIG. 1, the depolarizers of the invention
lined with an ion-permeable separator 2. The can is
?lled with the cathode depolarizer mix 6. A carbon rod
5 is inserted in the mix to provide electric contact. The
cell is sealed by an insulating washer 9‘, placed over the
60 carbon collector rod in a layer of hard wax 4.
The cathode depolarizer mix is suitably prepared, for
example, from a mixture consisting of 10 grams of tetra
methylammonium itetrachloriodide, 8 grams of acetylene
a-Picoline
'y-Picoline
8-methylquinoline
Pyr‘rolidine
E. Other Amines:
(a) Triiodide (13-)
Benzyl amine
Dibenzyl amine
Tribenzylamine
(b) Tribromide (Br3*)—Tribenzylamine
(c) Dichlorobromide (BrC12-)—
A metal
contact cap 7 is placed on the rod.
Quinoline
N-r'nethylpyridine
Collidine
Tetramethyl phosphonium tetrachloroiodide
Tetramethyl phosphonium triiodide
Tetramethyl phosphonium dibromoiodide
Tetramethyl phosphonium dichlorobromide
Tetramethyl phosphonium diiodochloride
Tetramethyl phosphonium diiodobromide
Tetramethyl phosphoniurn dibromochloride
Tetraethyl phosphonium tetrachloride
Triethyl methyl phosphonium tetrachloride
Trimethyl ethyl phosphonium tetrachloride
a GI can be incorporated in a cell consisting of a zinc can 1
Collidine
S-methylquinoline
6-nitroquinoline
Piperazine
Trimethyl sulfonium triiodide (CH3)3SI3
Trimethyl sulfonium dichlorobromide
Trimethyl sulr'onium dibromoiodide
Trimethyl sulfonium diiodochloride
Trimethyl sulfonium diiodobromide
Trimethyl sulfonium dibromochloride
Trimethyl sulfonium chlorobromoiodide
Triethyl sulfonium tetrachloroiodide
Tributyl sulfonium tetrachloroiodide
65
black and 20 mls. of a saturated ammonium chloride
solution.
Flat reserve cells may use the mix, as shown in FIG. 2,
which shows the con?guration and construction of ?at
cells in which the organic depolarizers of the invention
70 have been demonstrated to operate with great success.
The depolarizer material may be included in the cathode
plate construction or inserted between the cathode col
lector plate and the separator in electrical contact with the
cathode lead.
The anode 1 and cathode 6 may be connected through
75
3,057,760
7
an external source whereby the cell commences to be dis
alkyl and aryl substituted ammonium cations are the most
desirable soluble salts in the electrolyte. The electrolyte
is prepared by dissolving the desired salt in water or other
solvent. The concentration is not critical, and depends
charged by electrochemical action. The cell reactions
proceed essentially as follows:
(Anode reaction)
2Zn—>2Zn+++4e_
largely upon the salt combinations used. The most de
sirable concentrations are between 1 molar and saturated
solutions at ordinary temperatuers. Examples of soluble
salts useful in this invention are lithium, sodium, potas
sium, rubidium, cesium, calcium, magnesium, strontium,
ammonium, and alkyl or \aryl substituted ammonium chlo
rides and bromides. Immobilized electrolytes may be
employed if desired. When magnesium is used as the
anode, it is desirable to include in its electrolyte one or
more alkali metal, alkaline earth metal or ammonium
salts of chromic acid as corrosion inhibitors. The amount
of the corrosion inhibitor varies between 0.1 and 2 per
The above-described cathode reaction has been greatly
simpli?ed for the sake of illustration. Other reactions
may occur instead of or simultaneously with that shown
above. For example, a range of a four electron reduc—
tion of the anion can occur in which the iodine is reduced
in valence from +3 to —1 as follows:
(CH3)4NICl4+4e—> (CH3)4N++I-+4Cl—
cent of the electrolyte weight.
Cathode depolarizer mix.—-According to this inven
The overall reaction in this instance would be:
tion, the cathode depolarizer consists of an organic or in
Obviously, intermediate reduction reactions may occur 20 organic polyhalide wherein the oxidizing properties are
due to the polyhalide groups chemically combined in said
as well. Many factors, e.g., current drain and pH of the
substance. For increasing electrical conductivity of the
electrolyte, will determine which reaction or combination
of reactions occur.
cathode depolarizer, materials such as acetylene black or
Nevertheless, for the example given here, the overall 25 graphite may be used in an amount ranging from about
20 to 70 percent by weight of the mix.
cell reaction observed in practical applications may be
written thus:
For certain deferred action cell applications, princi
pally where long shelf life is required, it is desirable to
omit one of the essential components until need for elec
This reaction represents 72 percent of the theoretical ca
trical energy has arisen. The primary cells of this inven
pacity of the depolarizer based on a 4-electron reduction 30 tion are convertible into such cells, by simply omitting
to a practical cutoif voltage of 0.9 volt. Performance of
the electrolyte until just prior to use. To avoid aggra
such cells having organic polyhalogen depolarizers is
vated anodic corrosion conditions in deferred action cell
shown in FIGS. 3, 4 and 5 contrasted therein with the cells
applications, the anode can be additionally protected by
having the same depolarizer volume using conventional
a thin coating of a water-soluble material such as poly
depolarizers in the same construction, with the same con 35 vinyl alcohol. Upon contact with vaqueous electrolyte,
ditions of discharge.
(the ?lm dissolves and the cell is ready for use.
Table I below contains representative examples of ex
An0de.—-The ‘anode for the primary cells of this inven
tion may be zinc, cadmium, iron, aluminum or magne
perimental cell systems utilizing the depolarizers of the
sium or other active metals or alloys or other active or
ganics (e.g. hydroquinone). Zinc or magnesium-based
40
alloys may also be used as anode material. In round cells
the anode metal may be the cell container, lining for the
container, a separate structure inserted into the con
subject invention using various amounts of a ?nely di
vided carbon (acetylene black) the balance of the de
polarizer mix being the polyhalogens. Table II shows
discharge data on reserve cell applications of these de
polarizers.
TABLE I
Polyhalogen Depolarizers Laboratory Test Cells
Cathode
Electrolyte
Carbon
Type
Percent
Compound
KIOl _________________________ _. AB,133
(OHQrNICh---
Anode
Metal
Type
Zn____ KCl..___
AB, 3a._
_ _
Piperldinlum IClr ______________ __ AB,
._
11.--. NIEI4CL-
Voltage
Vol. 0.0. 0.0.
100
1.57
5.5
200
1. 79
1. 70
12. 0
200
200
200
200
200
1. 75
1.02
2. 21
1.86
2.00
1.35
1. 41
1.90
1.38
1.64
8.4
5.4
as
3.0
2.0
200
200
1.70
Res.
Ohm
1.96
1.92
1.61
2.0
1.58
3.0
tainer, or in the form of powdered metal. The anode 60
may be in any geometrical con?guration desired.
Separator.—-It is necessary to separate the anode and
cathode from each other; to accomplish this, a separator
may be inserted between the two, although other methods
Discharge Dam
Cathode Compound
I
of separation may be used. The separator may be any 65
,
ionically permeable, natural or synthetic, material com
patible with the electrolyte and depolarizer such as paper,
Km], ________________________ __
plastic, methyl cellulose, carboxymethyl cellulose, cello-
(ogahglglhn-
phane, polyvinyl acetate, or a starch gel or a combina~
a er
P P
~
_
_
A
E?
150
mp.,
750
-- 28 223.3
'
Porous ceramics or 70
other inorganic structures may be used in the place of the
Capacity
CD
Amp, met/é. Ina/0'0. min/g. Percent
'
tion of several of such materials.
CD
150
750
220 1,100
3, 5
20
.
3_97
29,3
‘114.88
25.0
315
15175
1285
ms
38,8
92
_
50
250
2.83
10. s
65
~Picolin1um I014.
50
250
2.83
4.25
24
Pyrro‘lldinium IC
50
250
2.83
Electrolytes.-The electrolyte may be an ionized solu-
P111er1d1n1umIOh--
tion of a soluble salt or salts. Bromides and chlorides of
the alkali and alkaline earth metals and ammonium and 75
‘Acetylene black
50
250
2-83
11.0
5-75
00
31-4
3,057,760
.
10
What is claimed is:
TABLE I1
I
1. A galvanic cell comprising an anode, ‘a depolarizer
cathode, and an electrolyte, said depolarizer-cathode con
taining a polyhalogen compound consisting of at least one
Deferred Action Cells
negatively charged component composed of at least three
Cathode
Polyhalide Depolarizer
_Mix1
.
Weight]
Cell, gms
0.0.
(CH3)4NI014 _________________________ __
(CH3)aNHIC14._ _.__.._.__
(CHzhNHzICLl ______ ..
12
l2
12
1. 84
2. 16
2. 16
CHaNHaI
____ ..
halogen atoms and a positively charged component se
lected from the group consisting of alkali metal cations
Voltage Initial
.
having {an atomic radius ‘at least equal to that of potas
sium and onium radicals of polyamines, heterocyclic
0.0. 2
1. 58
1. 33
l. 54
12
2. 09
l. 20
(GHzOaNICla...
12
2.02
1.14
IC _________ _.
12
2.06
1. 46
Pyndiniurn I01;
12
1. 92
0. 92
Pyndinium I014 .
12
1. 96
1.10
15
2. ()9
1. 75
Pyridinium EH01..."
Melamine 'I‘ri-(IOh).
15
12
1. 99
2.08
1.66
1. 42
Guanidinium I014. _ . _ .
l5
1. 88
1. 20
12
2.07
1.18
Pyrldinium BrClz___
_______ __
Plperazinium Di-(ICh)
.
Voltage
Regulanon-8.5
Polyhalide Depolarlzer
min., percent
Initial,
Current
Density
10
amines, arylamines, sul?des, and phosphines.
2. A galvanic cell comprising an anode, a depolarizer
cathode, and an electrolyte, said depolarizerecathode con
taining a polyhalogen compound consisting of at least one
negatively charged component composed of at least three
15
halogen atoms and a positively charged component com_
posed of an alkali metal cation having an atomic radius at
least equal to that of potassium.
3. The galvanic cell de?ned in claim 2 wherein said
alkali metal cation is selected from the group consisting
20 of potassium, cesium, and rubidium.
4. A galvanic cell comprising an anode, a depolarizer
cathode, and an electrolyte, said depolarizer-cathode con
taining a polyhalogen compound consisting of at least
one negatively charged component comopsed of at least
three halogen atoms and a positively charged component
25
composed of an onium radical of a polyamine.
5. The galvanic cell de?ned in claim 4 wherein said
polyamine is selected from the group consisting of urea,
Ina/sq. 1n.
guanidine, and the alkylenepolyamines.
(CH3) 4NIC/l4_ ..
(CH3)3NH C .
(CHs)zNH2I
CIIsNHaI
________________________ ._
_________________ .._
14 -_
14 . . _ . .
....... __ . _ _ _ __
:l:11. 8
5:8. 6
860
860
_
$14. 1
970
_
5:4. 8
777
(CHahNI 013..
_
:|:9. 6
780
K1014 ....... --
-
5:6. 6
691
Pyridiniurn 1C _
_
:1:6.4
Pyridinium 1014.
630
:1:1. 9
701
..... -_
:1:18. 2
1, 000
_
5:11. 5
879
Melamine Til-(1014)..
:1:11. 8
980
Guam'dinium 1014....
:1:11. 1
684
Piperazinium Di-(ICl; _.__
3:12.41
800
Pyridiuium Br012..
Pyridinium BrzOl ....... __
30
1 4c : 1 ratio depolarizer/ graphite.
35
2Fixed resistance external 1oad-—0.15 ohms, test at room 40
6. A galvanic cell comprising an anode, a depolarizen
cathode, and an electrolyte, said depolarizer-cathode con
taining a polyhalogen compound consisting of at least
one negatively charged component composed of :at least
three halogen atoms and a positively charged component
composed of an onium radical of a heterocyclic amine.
7. The galvanic cell de?ned in claim 6 wherein said
heterocyclic amine is selected from the group consisting
of melamine, morpholine, pyridine, pyrolidine, pyrrole,
piperidine, quinoline, picoline, collidine, quinaldine,
piperazine, ca?eine, and quinine.
8. A galvanic cell comprising an anode, a depolarizer
cathode, and an electrolyte, said depolarizer-cathode con
taining a polyhalogen compound consisting of at least one
negatively charged component composed of at least three
All cells ?at plate construction—anode and cathode
halogen atoms and a positively charged component com~
areas each approximately 10.2 square inches.
Anodes-powdered zinc type on supporting metal grid. 45 posed of an onium radical of an arylamine.
9. The galvanic cell de?ned in claim 8 wherein said
Separators-matte of plastic.
temperature.
Electrolyte-CaCl2 eutectic type (low temperature).
arylamine is selected ‘from the group consisting of benzyl
Regulation-Variation in voltage over ?rst 8.5 minutes
amine, dibenzylamine, and tribenzylamine.
of operation expressed as percent of total operating volt 50 ‘l 0. A galvanic cell comprising an anode, a depolarizer
cathode, and an electrolyte, said depolarizencathode con
a e.
Ti show the broad application of the subject depolar
taining a polyhalogen compound consisting of at least one
izers, a rechargeable cell construction was made using
negatively charged component composed of at least three
one of the depolarizers of this invention, speci?cally,
halogen atoms and .a positively charged component com
(CH3)4NICl4. Ten grams of the depolarizer were mixed 55 posed of a sulfonium radical.
with 10 grams of acetylene black and NH4C1 electrolyte
11. The galvanic cell de?ned in claim 10 wherein said
added to :form a paste. The cathode depolarizer paste
sul-fonium
radical is an alkyl sulfonium radical.
was then applied to both sides of a porous carbon plate
12. A galvanic cell comprising an anode, a depolarizer
which served as the cathode current collector. For test
cathode, and an electrolyte, said depolarizerecathode con
purposes only, two powdered zinc anodes were employed,
taining
a polyhalogen compound consisting of at least one
one on either s'de of the cathode construction. Plastic
negatively charged component compose-d of at least three
separators consisting of a material marketed under the
halogen atoms and a positively charged component com
trade name of “Dynel” were used to line the anodes.
posed of a phosphonium- radical.
About 80 cc. of NH4Cl electrolyte were added after the
13. The galvanic cell de?ned in claim 12 'Wherein said
electrodes were positioned in the cell container. The cell
was discharged and charged at 5 amperes for two cycles, 65 phosphonium radical is an alkyl phosphonium radical.
14. A deferred action galvanic cell comprising an
using only a part of the theoretical capacity (70 amp.
anode having on at least one surface a protective ?lm
min. or 7.0 amp-min. per gram of depolarizer) to main
tain operation at a relatively high, level voltage. Re
composed of a waterdsoluble material, a depolarizer-cath
sults are shown in FIG. 6. These results prove the
ode, and an electrolyte separated ‘from said anode, but
e?icacy of the subject compounds as depolarizers in a 70 placed so as to establish contact with said anode upon
rechargeable cell system.
From the foregoing, it is apparent that the objects of
actuation by external means, said depolarizer-cathode
containing a polyhaiogcn compound consisting of at least
one negatively charged component composed of at least
depolarizers has been found, which is of wide application
three halogen atoms and a positively charged component
75
in many cell systems.
the invention have ‘been realized and that a new class of
11
3,057,760
selected from the ‘group consisting of 'alkali metal cations
having anatomic radius at least equal to that of potas
sium and onium radicals of polyarnines, heterocyclic
amines, arylamines, sul?des, and phosphines.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,528,891
Lawson _______________ __ Nov. 7, 1950
12
2,566,114
2,874,079
2,874,204
Block ________________ __ Aug. 28, 1951
Lozier et a1. __________ __ Feb. 17, 1959
Morehouse et a1. ____-____ Feb. 17, 1959
FOREIGN PATENTS
240,140
461,350
Great Britain _________ __ July 15, 1926
Canada ______________ __ Nov. 29, 1949
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