CA1271217A - Cell corrosion reduction - Google Patents

Cell corrosion reduction

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Publication number
CA1271217A
CA1271217A CA000501694A CA501694A CA1271217A CA 1271217 A CA1271217 A CA 1271217A CA 000501694 A CA000501694 A CA 000501694A CA 501694 A CA501694 A CA 501694A CA 1271217 A CA1271217 A CA 1271217A
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Prior art keywords
anode
metal
cell
organic phosphate
grains
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA000501694A
Other languages
French (fr)
Inventor
Purush Chalilpoyil
Frank E. Parsen
Jesse R. Rae
Chih-Chung Wang
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Duracell Inc USA
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Duracell International Inc
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Publication date
Priority claimed from US06/749,688 external-priority patent/US4632890A/en
Priority claimed from US06/764,454 external-priority patent/US4585716A/en
Application filed by Duracell International Inc filed Critical Duracell International Inc
Application granted granted Critical
Publication of CA1271217A publication Critical patent/CA1271217A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/04Cells with aqueous electrolyte

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

CELL CORROSION REDUCTION
ABSTRACT
Gassing is significantly reduced in electrochemical cells having anodes of metals, such as zinc, by reducing the number of grains in the particles of the polycrystalline metal to at least a third of the original number of grains and thereafter using the metal in the formation of the cell anode. Such grain number reduction is effected by heat treatment of the anode metal at a temperature below that of the melting point of the metal. Corrosion is further reduced with such reduced grain number particles and particularly with single crystal particles by the addition of small amounts of a gas inhibiting surfactant, for example, an organic phosphate inhibitor such as RA600 from GAF Corp. to the cell.
Alternatively, or in addition, corrosion is reduced by prealloying the metal particles with small amounts of one or more of indium, thallium, gallium, bismuth, cadmium, tin and lead prior to reduction of the number of grains or the formation of the single crystal particles. A
synergistically lowered rate of corrosion and cell gassing is obtained even with reduction of mercury content.

Description

This inveDtion relates to methods snd matesials u0ed for reducing gassing in electrochemical cells as vell as the amount of mercury required in anode amalgamations for such cells.
Uetals such a8 2inc have beer, com~onl~ utilized as anodes in electrochemical cells, particularly in cells with aqueous alkaline electrolytes. In such cells the zinc is amalgamsted with mercury iD order to prevent or reduce the e~tent of reaction of the zinc ~ith the aqueous electrolyte with the detri~ental evolution of hydrogen gss. In the past it has been necessary to utilize about 6-7% by ~eight of Qercury amalgamstion in the anode to reduce the amount of "gassing" to acceptible levcla.
~owever, becau~e of environ~ental considerationa it has become desirable to eliminate or, at the very least, reduce the amount of mercury utilized in such cells but without concomitant increase in cell gassing, Various ezpedienta have been utilized, to achieve such mercurg reduction, such as special treatment of the zinc, the use of additives and e~otic amslgamatioD methods. ~owever, such methods have either had economic draYbacks or limited success.
It is sn object of the present invention to provide an econo~ic means for reduction of gas~ing in electrocbemical cells.
It is a further object of the present invention to provide a relatively economic means for permitting the reduction of a~ounts of mercury used in amalgamation of aqueous electrochemical anode ~etals without significant CoDCOmitant increase in cell gassing or reduction of cell performaDce.
These and other objects, fe~tures and advantages of the present invention ~ill become more evident from the following discussion as well as the "drawingsn in which:
Figure 1 is a photomicrograph of cross aectioned polycry~talline zinc particles; and Figure 2 is 8 comparative photomicrograph of cross sectioued polycr~stalline zinc as treated in accordance with the pre~ert iDveDtion.

~L~7~Z~7 Generally the present inv2n~ion co~prises a method for malcing an electrochemical cell, with rednced gassing. The invention fnrther comprises the cell containing the treated anode materisl. The method of the present invention generally comprises reducing the number of grains in the polycrystalline anode metal to one third or less of the ori~inal number of grains. There~fter, the reduced grsin anode metsl is formed into an anode auch as by colDpression of powder particles either on a substrate or within a cavity. Alternatively, the aDode metal may be in the form of a sheet witb the anode being convolutely wound in a "jelly roll"
configuration together with the cell separator and cathode. The sheet metal may alDo be u~ed, ~ithout ~inding, in a prismatic cell, If desired, the anode metal (particulsrly rinc) iB amalgamated ~ith mercury after the grain reduction and prior to placement of the anode metal in the cell. In all the aforementioned embodiments, with such ectent of grain reduction there is a concomitant reduction in the e~tent of grain boundaries and a reduction of gassing at such sites.
To further reduce the e~ctent of gaAsing 8 small amount of a surface acti~e heteropolar substance (#urfactant) of a type that lill sct aD a hydrogen evolution inhibitor is added to the cell. Because of the heteropolar nature of the surfsctant it is generally at lesst slightly soluble in the cell electrolyte and hAs a polar affinit~ eo the surface of the anode metal particles vith a coating being formed thereby. Such nffinity is psrticularly marlced ~rith respect to zinc particles commonly utilized in snodes of alkaline electrolyte cells. The surfactant sllsy be effectively incorporated in the cell in various ways. For e~arple, it may be added to the anode, incorporated in the electrolyte, or in the qeparator by pre-wetting or impregnating the separator with the additive.
The surfactsnt may eYen be added to the catbode. In all such instances the surfactant migrstes to the surface of the snode meeal particles to form the requisite hydrogen gas inhibiting coating. Adding the surfdctant to the anodic materisl is by direct addition to the powdered ~etsl tamalgamsted or unallalgam~ted) to form a surface costing for the anode ~.~7~1L2~

metal. Alternatively, the surfactant i~ added to the electrolyte whicb is then admi~ed with the anode metal particles vith resultant migratlon of the ~urfactant to the surface of the anode metal particles. Migration of the ~urfsctnnt to the anode metnl pArticles may also be effected by the addition of the surfactant to the separator or the csthode.
Alternatively, or in addition, the anode material p~rticles, auch 88 ~inc, sre prealloyed with a smsll amount of one or more of indium, cadmium, gallium, thallium, biamuth, tin, and lead and then changed into particles with reduced number of graiD~ or ioto individual discrete single crystal psrticles which are thereafter amalgsmated with mercury.
In order to effect reduction in the number of grains, polycr~stalline anode materials such as zinc are heat treated at a temperstur2 belo~ the melting point thereof for D &ufficient time ~hereby the number of grsins in the polycry~talline material is rednced to one third or le~s of the original material.
Though the anode maeerial remains polycrystalline sfter thi6 heat treatment, the amount of grain boundsries are reduced with the reduction in number of grains. ~8 a result, the amount of 8as~ing in the cell, with the treated particles, is markedly reduced ~ince it is the area of the grain boundaries vhich iB most conducive to high chemicsl activity snd gas formation. In addition, mercury infiltrates into grain boundaries reAdily.
With the reduction of grain boundsries there is a reduction in the amount of mercury required for amalgamation ~ith the anode material. ~ith the reduced Brain anode m&terials the amount of ~ercury required for amalga~sation can be effectively reduced from &bout 6-7Z to up to about 4Z.
~ eat treatment of the anode material is dependendent upon the factors of purity of the polycrystalline atarting materisl, the temperature at which the heat treatment ia effected, and the duration of such heat treatment. It is understood that heat treatment of powder particles of different bulk quantity may differ in length of ~ime requiret since the interior of the aggregate is somewhst insulated by e~terior ~aterial and does not "soe" the sa~e amount of heat as e~ternal material in direct receipt of the heat. In practice, a contiDuou~ tumbling calcined furnsce ~7~

~ill provide mo3t effective heating snd ns a result, with properly desigDed cslciner, less thnn teo minutes at temperstures sbove 370~C i8 ~ufficient to effect sufficient grain reduction. ~ecry~tsllization and grain coarsening depeDds UpOD maDy factors such as temperature, time, strDin energy ~ithin tbe materisl, snd the purity. As a result, e~sct heat treatment psrA~eters are determined iD accordnnce with the specific heat treatment equipmeDt being utilized. For clarity, the effect;ve heat nnd temperature, hereinsfter referred to, relste to a direct applicntion of heat to the material. In all ewents, a reduction of the number of grains in the material to one third or less of the original material is the desired result.
The heJt treatment of the polycrystalline snode Tnaterinl i8 effective with both powdered materisl generally used in the construction of compressed anodes in cells hsving a bobbin type structure, nnd such treatment is alao effective ~rith respect to the treatment of metal strips or aheets utilized in prismatic or con~oiutely wound cell structures.
The purity of the initial polycrystalline anode mnterial determines, in part, the length of time required to provide the requisite reduction of grain~ or conversely the temperature st ~hich the material should be heated for n given period of time; the lo~er the purity, the higher the temperature or the longer the time period required. The ~ost co~on snode materisl for electrochemicnl cells is zinc with the ~o~t common impurity contsined thereio being lesd. Other, le~s co~mon, snode materiala include cadmium, nickel, magnesium, Yluminum, manganese, calcium, copper, ironj lend, tin and mixtures thereof including ~i~tures with rinc.
The ~lkaline electrolyte solution in uhich the anode maeeridl i~ placed and ~Ihich generallv iB a factor in tbe gss generstion (usuallY the anode rescts with the electrolyte with resultant ga;i formation) is usually sn squeou3 solution of a hydro~ide of slknli or alkaline earth metAls ~uch as RaOH snd ~01~. Common cAthodes for the alksline cells include manganese dioxide, cadmium oxide and hydroYide, mercnric o~ide, lesd oxide, nickel oxide snd hydroxide, silver oxide and oir, The reduced grain number anodes of the present invention ho~ever are Also of utilit~ in cells haYing other electrolytes in ~/hich gAssing of the anode is problemstical ~uch as in acid t~7pe electrolyte3.

~ ~7~

Co~oa al~aline t~p~ c~ contai~ compre~l~2d pol~cr~tallin~ lC
particl~ ha~ ag ~er~e particlo ~ o about 100 ~icron~. ~elb o oueh pasticle~ h9~ ~'DoUt 16 or 2~0r~ ~5rl~iD~a aDd isl aceorda~co ~Oieh t~
pre~2nt in~ontioll t~e nu~ r of gr-in~ e~ch of the p~rticl¢~ i~ red3ced by h~tin~ tho ~i~c psreicl~ ~t ~5l offect;vo teDlpes~tur~ bet~eD ~out 50 to 419.5~C (th~ lstter bei~ th~ ~ltiD~ poin~ o Zi'tlG~ for perio~l of ti~ ra38ia~ fro~ ~bot~t t~o hour~ At 50C to IdbO~lt fiv~ ute~
at 419.S~C to reduco th~ Ot o~ ~rai~l to a~l BV-3r~,B of abo~t 3 to 5 gr~ per p~r~ciel~. Zi~c p~rticl~ll h-~iD~ lesd i~puriei~o reqllir~ A
te~p~r~tur~t of ~bo~t lO0-C fo~ tha Y~ini~ tllO hou!~ p~riiod to schi~
~i~ilar r~d~etio~ r of ~rs~.
ul ~urf~ct~ntl~, ~ich G~gl bs sdd~ to t~ eelllD is ccords~c~ vit~
thq pre~e~ u~ion i~ order to furth~ se~l~cls t~ de~reat of il~clude ~h~len~ 03ido co~t~in~ poly~r~ 3tlC}1 a~ t~O~d~ h~ g pho~phst~
group~, DlatU~:lAtea or u~aaturated ~noc~r~os~lic acit ~ie~ a~ le~t tvo e~sol~id- l~ro~ 3; tritae~los~po1~(ethyl~o~) et~ol; an~ t pr2f~r~bl~ org~i¢ pbo0p~t~ ~tes~. ~hoe pr~ferz~d or~ ic pl~oJph~t~
e3s~r~ gen~r~lly llr~ ~1119a~ SIII or ~ic3a~r~ tl~a follo~ fOn~31B:
~0(3tO)~ C ~ P - ~9 (I~S)~
~h~r~ ~ 4 ~ ~ 3 X ~ Il, a~Dnisg ~i~o, or ~ ali or alE:ali~ ~s1rth ~tsl h~ r ~ 1 or ~ yl of 6-~8 el~rboll ~to~
Sp~eif~G u-~l o~ga~ic po87~a~ t~ sur~lets~ts iDelu~a s~~ ri~ls vhich cæ~ bo ill~nt}fi~ Dy th~i~ e~rcial a~.~ip~t10~ 600 (U~
~nio~ic o~ c pl~o0pb~ t~r up ~ r b~ d o~ sr ~ris~r~ slco~ol, ~ a u~str~ sl p~sgf~l o~t3r o~ p~o~pho~e aeid3; 1~ ~610 ~ 10llic c~pl~ org~e p~o-p~e~ ~t~r ~u~ll~ by GU Cosp. ~ th~ ~re~ aci~ g 8~ ~r~tic h~d~o~o~, aaa 1~ u~a~ersl~d par8i~ r o~ ~hosy~hosic acid);

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aD~ A3lPAC ~--040 tul soio~io ~llo ~titt3te~ o~ebo pl~8~ C~i3 oBt~s i~ bg ~ 1~ d~ Cor~

1;~7~

It h~ been found eh~t the iDcorporation of a ~urfJctD~ sdditi~e of tho typ~ referre~ ts her~i~ in ~ c~11 iD ~ n-o~nt of fro~ O-OOlS to 5~ preferaSly O.OOS to 1~ snd 20Dt prefer~bly 0.01 to 0.3S by Yeight of the ~CtiY~ ~DOd~ oo~pon~t of the cell, precludea or ~t lc~at ~i3Dific~6a~1~ iD~i~ie- tk~ o~olutio~ o hydrog~n ~ithi~ th~ coll, s~d thercb~ Lncre~e ito ahelf life ~d its u~ful vor~ lif~.
Th~ ~tditio~ of th~ sur~ct~at ~4 c~ eo~t~i~iD& rsd~ced u~ber of DOdO ~ dl g~iD~ or ~iD~l~ o~t~l~ of uc~ ~od~ ~tal~ pro~id~s -~Ger~i~eie fur~h~r red~e~ioa ~f c~ll g~ei~S.
~ ho~6~ eh- U~2 of ci~ cr~atal anod~ ~stsri~1 ~n~ t~ u~ of or~a~ic phospb~ta ~t~r ~ur~-c~s~t~ (~8 P~t~e ~o-. 4,4~7,6Sl ~nd ~,195,120 o~ned by th~ 8aa~ ig~o~ ~ th~ pr~3~ne iD~tioa) b~v~ ~ep~ratolg bQ~ ~DDND
~o ef~cti~ red~e~ cffll g~s~io~ or to p~r~it ~GUY r~uction o ~rcur7 cont~Dt i~ t~ ~n~a- ~ith4~ ~str~ent~ ere~o i~ 8~ 9 t~ effoce 4f th~ coD~i~a~io~ has unexp~et~dl~ 5e~n di~co~6r~a ~o be co~oider~bl~
r- th~n ~ddit~Y~. Tb~, in esll~ n8 ~s~ m~t~d ai~6lo cr~Jt~l ~iDs ~ode~, tha ~sou~t of ~-reur~ i~ th~ 6~ c~ b~ ~ff~cti ~l~ r~dnc#~
ros abo~g 6-7~ to ~bo~ 4~ or ~t~t~ di~f~re~ be r~t~ of ~00in~ o~
~ol~cr~t~ aa~l~ CoRt~ 1.52 ~Qrc~r~ C2~ bo red~c~

~bo~t 2-fol~ ~t~ t~ u~ o~ aiD~l~ cr~ot~ c. SL~ rl~ th~
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u~ilisatioa o ~ or~oic ~ho~ha~3 o~tær ~s~eta3t ~eh ~ GU~a ~600 i~h pol~er~t~ ioe ~13~a ~o~a r~sl~ bo~ ~ 4 fol~
TM
r~t~ct~ o~ ~sa-iD~ ~it~ for ~$a~ ol~ G U ~C ~600o ~o~ r~ ~a ~ccord~c~ h tb~ ps~ g i~ eio~ a co~b~Datio~ of t~ t~o~ . 8 ~iD~le cr~e~l si~e us~l~a~ ~ith ~ ~rfsc~a~t u~p~et~ p-r~igs ~b~
~f~cti~o ~d~ct10D o th~ ~e~corg to ~bo~e 1.5S ~igh 4bo~t ~ 20 ~old ~o~ ra~ iahibi~io~ or ~bo~e ~bl~ ~h~t ~l~bt ~o b~ poet~ o 8 ~tt~r 0~ co~r8~, Co8~iD~io~ 0~ ch~2ic~1 gao rsd~ctio~ di~t~ doe~
~ot u~ually 3~ p;o~ D ~dit~Y~ Ct ~0~ do~ c~o~ ti~ tiD~
o ~dd~ . Yh~ u~- o~ tb~ ~r~c~sa~ ~se~rial ~itb ~ red~e~d ~rs~
~b~r ~ ao~ tor~1 p~9~ c~c~i~8~ r~ e ~ e~io~ ~
e~ ~b~ thB~ o~ ith 8~ ry~e~ ~t~ l b~lt lo~ th~C o~in2~ ~ie~ tho hi~ ~ra~ ~u~ al~cry~ co '7 The ~iDgl2 cryst~lc of zinc ~re preÇer~17 prep~red ~a d~3cribed i~
~id ~S PaCent No, 4~487,651~ Such procedur~ olve~ tho fo~atio~ o ~
thi~ ~kin crucibl~ o~ e~c~ o~ t~ siac particle~ by o-idl~tion in ~ir ~It u te~per~tur~ juae belo~ t~ ltisu pcis~ (419C) o t~Q ~i~c, he~tiD~ o tb~ enclo~ inc p~rticl~!a in ~ inerg at~o~pher~ ~07~ the ~eltiDg poln~ of the si~c a~d slolv cooli~8 th~r~-~t~r ~7i h r~oval oiE the oxite aO ZiDe particl~ o~ ge~rall~ r~8- b~t~ 80 ~d 600 ~icroola ~or utilit~ i~ electrae~ic21 cclls ~l~d ~uch ~etho~ provit~s D~a eff~ctiv~
o~a~6 for ~ iDSl~ cr~l~t~l p~rticlG~o ~f l~ueh ~11 di~ io~.
T~ DOU~ of s~rcur~ iD tl~- A~ R u~lg~ ~ r~ fros~ 0 - 4 depe~d~Ds upo~ t~ e~ll utill~tios sud t~ d-~re~ o~ oin~ to b~
tolor~lt2d .

~lgs~t~d s~duc~ ~r~ ~iber or sin~lq er~l~t~ t~l p~rticlo~
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~rith ~urf-ee~l~t ad~i~*~ æeh ~c ~C 8~600 3re fOQIl~d into ~ e~ for ~loetroeh~nie~l e-llD p-rtieul~rl~ Allcali~ etroeh3~ieal c~
ti~ h~ as~ ~o~d ~Fro~ eh~ r~d~c~ ~r~i~ 3ugib~r or cr~sC~ Q~ partielco ~ t~ ~rfsletult ~i~r~ th~r2to r~
oth6~r c-ll eo~on~e~ uch ao t~ ~l-c~Pol~e~, s~r~eor or cathod~ to vhieh th- ~r~aet~ta ~ itially d~lo Ot~r 3D0 c~p2bl- o b~ fon~ O r~dues~ ~,r~ a~b~r o~ ÇliD~llll Cr~8~
po~r~ Dd Qhish ~rc u~ ctro~sis~l c~ iucl-ada ~1, Cd, Ca, Cs, l~b, 19~ D ~Ut ~3D -~ ~urth~r l~ itiOl18l or al~cr~dt~ 8a~ 8~ for r~otlol3 o ~i~ th~ llo~i~ o pol~e~ e~lS~ O~ t-l p~rticl~ ~sith ~ or oth~r ~iLti~- prior to ~aod~ ~-t~ ,r~a~ r~d~cti0~ or t~ lEor~t~0l3 of th~ ,lo er~t~ t~l par~ eal~rally iD D~U~t~ ~Do~i~ b~t~s 2S-5000 p~s ~$~ ~r~bly l~tq~ 10~1000 p~ ~o~t o~ ~rGtlLr~ i~
~ asod~ r~ f~9 0 - 4g d$~ u~o~ t~ c~ll u~ eios ~a th- ~3rs~ oE ~ S ~O ~- eol~ra~

~L2~ 7 The amalgamated single cryatal ~etal particles uith prealloyed inclusions of materisls auch as indium are then formed into nnodes for electrochemical cella particularly alkaline electrochemicsl cells. Other anode metals capable of being formed into single crystnl powders and which are u~eful in electrochemical cells include Al, Cd, Ca, Cu, Pb, Hg, Ni, and Sn. It is understood that with anodes of these ~etsls the prealloy material is not the sa~e as the anode active material but iB less electrochemically Dctive.
In order to more clearly illustrate the effectiveness of the present invention in reducing cell gsssing, the following comperative e~amples are presented. It is understood that such e~amples are for illustrative pnrposes only and that details contained therein are not to be construed as limitationA on the present invention. Unless otherwise indicated herein and throughout the present specification all parts are parts by veight.
EXAMPLE
Three batches of polycryDtalline rinc of average particle aize of about 100 microna are heat treated for varying periods of time and temperatures and are then amalgns~ted with sbout 4~ mercury by veight. A
fourth batch of 41 mercury amalgamated polycrystalline zinc is not heat treated and is used as a control. Ivo grams of each batch are placed in 37I ~O~ solutions tsimilar to the electrolyte of al~aline cella) at 90C
vith heating parameters and gsssing rates given in Table 1:
TABL~ 1 Zinc Tre~tment Dl gaB (24 hours) ~1 ga~ (93 hours) Control, not hested 0.62 3.77 114 hours at 400C 0.25 2.07 235 hours at 400-C 0.28 2.78 70 hours at 419-C 0.28 2.18 It is evident froD the above that the heat treat~ent of the present invention serve~ to more than halve the gDssing rate of a~algamDted zinc. It is further evident that continued long term heating does not ~ignificantly affect 8assing rates and ia generally economically unde~irable.

Polycry~talline zinc powder (a~erage particle size of 100 microna) from the Ne~ Jerse7 Zinc Co. (~JZ) is heat treated at 370'C by tumbliDg for one hour in a rotating calcine furn~ce. The powder, as received from NeY Jersey Zinc, has the crystalline structure sho~n in Figure 1. After the heat treatment the po~der has the crystalline structure shown in Yigure 2 ~herein grain size is markedly increased, the number of grains is rednced und the smount of grain boundnries is concomitantly reduced. The polycrystnlliDe rinc, as received and after heat treat~ent i~ amalgamated Yith 4~ mercury and t~o gram snmples of each are tcsted for gassing as in Erample 1. ~n additional tvo gram sample of 7Z mercury amalgamated zinc from ~oyce Zinc Co., Yith similar polycrystalline grain structure and average particle size, is also tested for gassing a8 sn additional control (representiDg prior art amalgamated rinc) with gausing results given in Table 2:

Zinc Type Gassing (ml) after 24 hour- at 90C

AB receiYed from NJZ 4Z ~g 0.ô5 heated ~t 370~C for 1 hour 4~ ~g 0.4 7Z ~g Royce 0.25 Eent treatment, as described, provides an anode m~terial having markedlv superior gssning properties ~hen compsred to untrested polycryutslline zinc and slightly worse than prior art amAlgs~ated ~inc having considerably more mercury in the amalgam.

T~o grams of each of the amslga~sted zinc materials of RYample 2 are similarly tested for gassing at 71-C after periods of 7 and 14 days ~ith the results given in Tables 3 and 4:

Zinc Type 7 Duys (~1 gas) 14 dags (ml gas) As received from NJZ 4~ Pg 0,9ô 1,95 'dested st 370-C for 1 hour 4% Bg 0,50 1,19 7~ 'dg ~oyce 0.46 0.95 TA U ~ 4 Zinc Type Gassing Rate (ul/gm-day) 0-7 Dsya 7-14 dnys 0-14 days A8 recei~ed from NJZ 4Z Lg 70 69 70 ~eated dt 370'C for 1 hour 4~ ~g 36 49 43 7~ Ng RoYce 33 35 34 _g_ Both ~he toe~l U~ t of e~olve~ ga~ ~nt the 8s~ing rate of he~t treate~ ~inc po~t~r~, after e~:teu~ period~ of ti~ re comp~ o tho~e of sinc pov~r3 e~lga~at~ l~ith igDifics~tly ~oro ~ercur7.
It ia e~id~t fro~ eh~ p~oto~icro~r~phl~ of i!'igUrQ 1 and 2 t~ the nu~ero~ polycryst~lline gr~i~ bound~rie~ h~ becn reduced i~ nw~lh~r ~ith ~ concositult r~d~ct~oa i~ th~ er o pol~cryst~ o 8rsin~ per particle ithout gener~l ch~n~ tbe ~h4p~ o th~ iadi~id~al p~rticles~
rb~ nu~ber of gr~ io t~ he~t t~e~t~t p~ticlo~ i8 a thir~ 09: le~ OP
t~t o ehe origizul p~rti~lca.
!SS~Llt 4 Zi~e ~oe~r 81~ D cont~iniD~ 1.5S ~re~ry a~ it)l llt~d~râ
gr~i~ pol~cry-tAllin~ e ~lo~, ot~d~lrd gr~ olyer~l~tslli~ e ~i~h O.lS ~600 ~- an ~dltiY~ e~t, ai~gl~ er~eal ~ e, nd 5ia~ r~Qt ~ine ~it~ O.lS ~600 ~ 3~ ~ti~v~ ~ls~s~t. ~qual u90u~e~ of t~e uaal~a~a po~s~ ~r~ e~ 8Coe~l io equ~ ou~t~ of 37% ~:011 al1~1iD~ oolu~ion (t~pieal ~l~et~ol~t~ ~olueio~l o~ 211taliD~ coll~) ~ te~lte~ or ga-~iRg ~t tesllper~t~rs~ of 71~C. ~h~ O.lX ~C R~600 i~ dd~ ~o th- ~lk~

~olutioY~ tirriDg o t~ e lsl hueh ~olu~oo r~ule~ t~
depooi~ioo o~ ~h~ a6t~t o~ ~h~ siae. Th~ ~u~ o ~ is8, ~-s~r~ed in ~icrollt~r~/~r~ p-r dl~ L/~ay) ~d th~ raeu r~d~ctio~ ae~or~
(~ith t~ ol~cr~ liEw s~i~c co~atrol b~ r~ 8i~: forth ~ T~l~ S:
~I~ 5 ~OD~ 1; QUl~ C~IO~ CTO~
Polycry~tsll~ 3in~, 1.5S ~ 29S
Pol~crgatall~ si~c, loS~ ao 3~7 ~600 Si~l~ c~t~ iDC,, l .S~g ~ 14~
~iD~ls cr~s~al ~i~c, l.SS ~ lS 19.7 0.~ 01 ~ r~e~ ~tact~o~ s~t~ 8~ Jt ~ ~alt~ b~ ~l t~
b~ b~g 708 (307 8 2.1) go~ ~ c~ ue~ seio~3 o~ cr~otal ~i~o 8n~ ~600 ~ rato ~ lo~ eo n~ 3~ ~L/g-d~7O Th~

co~ stioa ~0~ 7~r ~ r~ ic~lly ~8~0C@B ~C)IIII ~5111~alill~ to ~bo~ doublo the e~p~ete~ s~c~tio~.

-1~

1~7~L'7 ~P~B 5 ZiDc po~d~s ~lguu of polgcryat~ a~:d DiDgl~ cs~-t~l ~inc ~ith TM
aut ~itho~t th~ 0.1% GU~C ~600 ~di~ ar~ te~t~d ao in B~ 3 ~ue ~ith 0.5~ ~reur~ aJul~u~ e ~ou~t of gaJ~iD~ 0~red i~
~icrolit~rllt~r~ p~r da~ (uL¦g-da~) ~d th~ r~t~ r~ac~ios f~etors (YiCb th~ pol~cr~ae~llin~ c co~trol b~iD6 1) ~r~ ~t fore~ i~ T~l~ 6:
T~l.B 6 ~IIOD~ ~T~ L GlU9I~G I~T~513~ ~D~CS~01l ~AC~O~
Pol~cr~st~ $islS, 0.5S ~g 720 Pol~cr~t~llias ~iae" 0O5S 8~ 130 S.S
o.~ 600 8~Dsl~ cr~ot21 ~c a O .SS ~ 26S

giI~gl~ cs~t~ c~ O~S~ ~26 2a 0 .1~ ~A600 ~ r~t~ r~etio~ faetor (i ~a~ ~o~l~ 8e ~fit h~ be~n ~sp~cte~l to b~ ~bo~ 14.9 (S.S ~ 2.7) for ~ eo~e~l otilis~ltio~ of ~iagl~ cr~tal ~i~o a~d 1~600 ~rith ~ooi~ rat~ r~d~c~io~ to ~bo~e 4~ t~L/g-d~g COIagiDatio~ hol~70r ~r~ ieall~r r~d~c~l~ th~ a~ to ~e~ doubl~
th~ e:-p~stQ~ r~ et~o1~.
It i~ a~ t ~o~ tho ll~O~- ~Ysspl~ d tsbl~ tb-t th~ ~l~a~
c~yct~ c vith o~ or s~r~ f~die~ul~ af D~ pr~ t in~ o~ i~
~dly ~f~ct~v- i~ p~r~itti~g 18r8~ Y~re~s~ re~so~io~ itl~ ~er~so~
iu c~ll 8 l~L~ ~
Pol~crgal:sllin- ~iao iu p~slloy~a ~itb SSO ~p~ of ~alli~a ~d 100 ppa o in~iuD. ~ fir~e ~ r~of iB ~h~s ~l~ loSS ~ rSOIr~o ~tCO~ I&~qp~ d8 into ind~i&o~ s~eal ~llo~ p~r~icl~9 ~
d~ocsib~ I~ o~r~9 psior to ~ ~tioa vitlb ~rc~r~G T~o ~r~ of ~ch of ~h~ B~~ are~ 8C~d ia a 37S 1~ eerol~:~ 801~0~ ~itl~ ga~oi~ ths ~d o~ 24 ~d 4~ ho~ta b~ B~ g?~ 11 b~ ei~ ~

oo~ro~io~. ~o co~trol ~ olger~lg~ e ~ith 7S
~re~ry ~ r to ~hae co~ly UB~ai illl al~ c~ . Beoult~ oS 1~1~6 tli~l~t5 dtlll 8i~@$ i~ S9~1dl 7 .

~7~

T~BLE 7 SA~PL~ - VOL~H~ OF GAS (mL), 90~C
24 Hours 48 ~our~
polycrystalline alloy 0.7 1.9 single crystal ~lloy0.3 l.O
control (7Z ~g) Q.2 0.5 2X~HPLB 7 A first portion of polycrystalline ~inc powter cont~ini~g 0.04~ lead is amalgamated ~ith 2X Hg and 3 ~econd portion i8 convert~d to individual single cry~tal particles prior to the a~Algamation. The amalgs~s are then tested for corrosion rate iD 10M ~O~ containing 2X ZnO~ The gassing raees at 71C ~re 225 uL/gm per da~ and 80 ~L/g~ per day reapecti~ely.
It is evident thst the corrosion reduction of snode metals such a~ ~inc by the prealloying with corrosion reducing additive ~aterials iB greatly enhanced by the formstion of single cryst~ls from the anode metal-additive alloy.
It iB understood th~t the above e~a~ples sre illuatratiYe in nature aad that chsDge~ in materisl treatment, m~terial proportio~a, the specific mAteriale, cell construction snd the like are ~ithin the scope of tbe pre~ent invention as defined in the follo~ing cl~im8 .

1~ .

Claims (18)

What is claimed is:
1. A method for making an electrochemical cell, with reduced gassing, with said cell having a polycrystalline metal anode subject to gassing, said method comprising the steps of:
a) reducing the number of grains in said polycrystalline metal to one third or less of the original number of grains;
b) forming said polycrystalline metal, with reduced number of grains, into an anode for said cell; and c) placing said formed polycrystalline metal anode into said cell.
2. The method of claim 1 wherein said polycrystalline metal is heated at an elevated temperature, below the melting point of said metal, for a time sufficient to reduce the number of grains in said polycrystalline metal to one third or less, of the original number of grains.
3. The method of claim 2 wherein said polycrystalline metal is selected from the group consisting of zinc, cadmium, nickel, magnesium, aluminum, manganese, calcium, copper, iron, lead, tin and mixtures thereof.
4. The method of claim 3 wherein said polycrystalline metal is zinc and wherein said zinc is heated at a temperature of between 50°C to 419.5°C for a minimum period of time ranging between five minutes and two hours.
5. The method of claim 1 wherein said method further comprises the step of adding a surface active hetero polar material additive having a polar affinity to said anode to said cell.
6. The method of claim 5 wherein said polycrystalline metal in converted to single crystals.
7. The method of claim 5 or 6 wherein said surface active hetero polar material additive comprises an organic phosphate ester having the formula:
[RO(EtO)n]x - P = 0 (OM)y where x + y = 3 M = H, ammonia, amino, or an alkali or alkaline earth metal and R = phenyl or alkyl or alkylaryl of 6-20 carbon atoms.
8. The method of claim 1 wherein said polycrystalline anode metal is alloyed with one or more members selected from the group consisting of indium, gallium, thallium cadmium, bismuth, tin and lead, prior to said reduction of the number of grains thereof.
9. The method of claim 5 wherein said polycrystalline anode metal is alloyed with one or more members selected from the group consisting of indium, gallium, thallium, cadmium, bismuth, tin and lead, prior to said reduction of the number of grains thereof.
10. The method of claim 8 or 9 wherein said polycrystalline anode metal is converted to form said discrete single crystal particles, whereby said one or more members form part of said single crystal.
11. An electrochemical cell comprising an anode, a cathode and an aqueous electrolyte characterized in that said anode is comprised of single crystal anode metal particles and said cell includes a surface active hetero polar material additive having a polar affinity to said anode.
12. The cell of claim 11 wherein said surface active hetero polar material additive is selected from the group consisting of ethylene oxide containing polymers, monocarboxylic acid with at least two ethanolamide groupings, tridecyloxypoly(ethylenoxy) ethanol, and organic phosphate esters.
13. The cell of claim 12 wherein said surface active hetero polar material additive is an organic phosphate ester having the formula:
[RO(EtO)n]x - P = 0 (OM)y where x + y = 3 M = H, ammonia, amino, or an alkali or alkaline earth metal and R = phenyl or alkyl or alkylaryl of 6-28 carbon atoms.
14. The cell of claim 13 wherein said organic phosphate ester is comprised of a member of the group consisting of the free acid of an anionic organic phosphate ester based on a linear primary alcohol, and being an unneutralized partial ester of phosphoric acid; the free acid of an anionic complex organic phosphate ester having an aromatic hydrophobe, and being an unneutralized partial ester of phosphoric acid; and an anionic mono substituted ortho phosphate ester.
15. The cell of claim 14 wherein said organic phosphate ester is comprised of the free acid of an anionic organic phosphate ester based on a linear primary alcohol, and being an unneutralized partial ester of phosphoric acid.
16. An electrochemical cell subject to reduced gassing comprising an aqueous alkaline electrolyte, a cathode and an anode comprised of mercury amalgamated single crystal zinc particles and an organic phosphate ester with said mercury comprising up to 4% by weight of said anode and said organic phosphate ester being comprised of the free acid of an anionic organic phosphate ester based on a linear primary alcohol, and being an unneutralized partial ester of phosphoric acid with said organic phosphate ester comprising from 0.01 to 0.3% by weight of said anode.
17. The cell of claim 16 wherein said mercury comprises up to 1.5% by weight of said anode, said cathode is comprised of manganese dioxide and said aqueous electrolyte is comprised of a potassium hydroxide solution.
18. An electrochemical cell comprising an anode, a cathode and an aqueous electrolyte characterized in that said anode is comprised of particles of discrete single crystals of anode metal and one or more members of the group consisting of indium, cadmium, gallium, thallium, bismuth, tin and lead, wherein said one or more members are present in said anode in a range of 25-5000 ppm and wherein said one or more members are alloyed with said anode metal, prior to formation of said discrete single crystal particles, whereby said one or more members form part of said single crystal.
CA000501694A 1985-02-12 1986-02-12 Cell corrosion reduction Expired - Fee Related CA1271217A (en)

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US70083685A 1985-02-12 1985-02-12
US700,836 1985-02-12
US749,688 1985-06-28
US06/749,688 US4632890A (en) 1985-06-28 1985-06-28 Anode metal treatment and use of said anode in cell
US764,454 1985-08-12
US06/764,454 US4585716A (en) 1984-07-09 1985-08-12 Cell corrosion reduction

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DE (1) DE3603342A1 (en)
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BR8600570A (en) 1986-10-21
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AU594661B2 (en) 1990-03-15
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IT1204791B (en) 1989-03-10
FR2577351B1 (en) 1989-09-29
GB2170946A (en) 1986-08-13
DK66886A (en) 1986-08-13
IT8619386A0 (en) 1986-02-12
NL8600347A (en) 1986-09-01
DK66886D0 (en) 1986-02-11
BE904216A (en) 1986-05-29
DE3603342A1 (en) 1986-08-14
NO860475L (en) 1986-08-13
IE860198L (en) 1986-08-12
CH671304A5 (en) 1989-08-15
ES551801A0 (en) 1987-07-01
NO169098C (en) 1992-05-06
GB2200791A (en) 1988-08-10
FR2577351A1 (en) 1986-08-14
SE8600606L (en) 1986-08-13
ES8706854A1 (en) 1987-07-01
GB2170946B (en) 1989-11-22
GB8603413D0 (en) 1986-03-19
NO169098B (en) 1992-01-27
GB2200791B (en) 1989-11-29
GB8802013D0 (en) 1988-02-24
SE8600606D0 (en) 1986-02-11

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