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March 5, 1963 J. G. E. COHN ETAL 3,080,444 ELECTRIC CELL Filed June 28, 1960 é'sneets-sneez 1 I I l I l I l I l FIG. I l l Reference leaf/0d? Mefal $200’! Z4 f2 5715M’ ‘I; 1. INVENTORS JOHANN c. E. coHN ANNA P. HAUEL II II ‘’ M zigrfw I ATTORNEYS March _5, 1963 J. G. E. COHN ETAL L~ 3,080,444 ELECTRIC CELL 2 sheets-sheet: Filed June 28, 1960 FIG.3 0.2 0.. 0.2 .BIJu<CoOZwA_kmaFJL 5 4 5 0 0. O. Oa 0.7 0.8 0.9 30 so O i 11m: (MINUTES) 2 I20 wJAVA; 0 BY Hw ? L.S. WTmNPl/EAT ?.3V6 Tfunau“CE01. v.-. wmm wa N AM w 5 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.