IE57432B1 - Cell corrosion reduction - Google Patents
Cell corrosion reductionInfo
- Publication number
- IE57432B1 IE57432B1 IE198/86A IE19886A IE57432B1 IE 57432 B1 IE57432 B1 IE 57432B1 IE 198/86 A IE198/86 A IE 198/86A IE 19886 A IE19886 A IE 19886A IE 57432 B1 IE57432 B1 IE 57432B1
- Authority
- IE
- Ireland
- Prior art keywords
- metal
- tha
- anode
- tho
- grains
- Prior art date
Links
- 230000009467 reduction Effects 0.000 title claims abstract description 12
- 238000005260 corrosion Methods 0.000 title abstract description 7
- 230000007797 corrosion Effects 0.000 title abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- -1 zinc Chemical class 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052716 thallium Inorganic materials 0.000 claims abstract 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 150000003138 primary alcohols Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 125000005842 heteroatom Chemical group 0.000 claims 2
- 241001307205 Atopos Species 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 235000014309 Eleocharis tuberosa Nutrition 0.000 claims 1
- 244000103152 Eleocharis tuberosa Species 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 235000014030 Podocarpus spicatus Nutrition 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052753 mercury Inorganic materials 0.000 abstract description 15
- 239000004094 surface-active agent Substances 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- 239000002923 metal particle Substances 0.000 abstract description 3
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 9
- 229910000497 Amalgam Inorganic materials 0.000 description 7
- 208000023514 Barrett esophagus Diseases 0.000 description 7
- 244000287680 Garcinia dulcis Species 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 210000004013 groin Anatomy 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229960002069 diamorphine Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- IJJWOSAXNHWBPR-HUBLWGQQSA-N 5-[(3as,4s,6ar)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]-n-(6-hydrazinyl-6-oxohexyl)pentanamide Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)NCCCCCC(=O)NN)SC[C@@H]21 IJJWOSAXNHWBPR-HUBLWGQQSA-N 0.000 description 1
- 241001116389 Aloe Species 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- 241000566113 Branta sandvicensis Species 0.000 description 1
- NYQDCVLCJXRDSK-UHFFFAOYSA-N Bromofos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(Br)C=C1Cl NYQDCVLCJXRDSK-UHFFFAOYSA-N 0.000 description 1
- 241000288673 Chiroptera Species 0.000 description 1
- 241000252233 Cyprinus carpio Species 0.000 description 1
- 101100055841 Danio rerio apoa1 gene Proteins 0.000 description 1
- 241000760358 Enodes Species 0.000 description 1
- 241000490229 Eucephalus Species 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- 101100001518 Rattus norvegicus Igfals gene Proteins 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 235000011399 aloe vera Nutrition 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002618 waking effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
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
Thin iaveatioa relate· te Method· aad Mteriala used for redociag gaaaiag ia electrochemical cell· aa well ac the «aoeat of mercury required ia eaede aaalgamatieae for each eelle.
Hotel· each ee aiac have hen eooaealy atillaed ae aaodee ia , electrochemical cello, particularly io eelle with aqueous elbeliae * electrolytes, la each cell· the aiac ia amalgamated with mercery ia order to prsvsat or redace the exteat of reactloa of the aiac with tha equeoae electrolyte with the detrimeatal evelutiea of hydrogea gas. Xa the pe»t it he· been aeceaeery to atiliie about 6-71 hy Might ot mercury amalgamatioa 1Q ia the aaede to redace the camuat of gaaaiag te aceeptihla level·.
However, because ef eavireameotal eeaaideratioae it hae become desirable to elimiaate or, at tha vary laaat, radaca the ameuat ef mercery atiliced io each cello hat without eeaeemitaat iaereaee ia call gaaaiag. Various expedieata have bee» utilised, to achieve each mercury redactioa, each aa 15 special treatmeat of tho aiac, tha wee of additive· aad exotie amalgamatioa method·, however, each methods have either had ecoaeaic drawback· or limited success· Xt ia aa object ef the preseat iaveatiom te provide eu ecoeoaic aeaas for redactioa of gaaaiag ia electrechemieal cello.
Xt ie a further object of the preaeat iaveatioa to provide a relatively ecoaeaic aeaae far permittiag the redactioa of aaeuatc of mercery used ia aaclgaaatioa of aqueous electrochemical aaode metals without eiguificaat eeacomiteat iaereaee ia cell gaaaiag er redactioa of cell perforaaace.
These aad other objects, features aad advaatagaa of the preaeat iaveatioa will become more evideat from tha fellowiag discuaaioa es well ac the drawioge io which: Vigors 1 is a photomicrograph ef crocs sectioaed polycrystalliae aiac particles; aad Figure 2 is a cooperative photomicrograph of cro·· cectioacd polycryatalliae siac ae treated ia accordance with the preaeat iaveatioa. -|Λ Generally the present invention coapriaea a «tW far making ra electrochemical call, with reduced gaaaiag. The invention farther comprises the call costaialag the treated aaoda material. Tha method of the praarat iavaatioa graorally comprises rodaciag the member of graiaa ia the pelycryetalliae aaoda ratal to ora third or laao of the erigiaal , aaabar ef graiaa. Thereafter, the reduced graia aaoda ratal ia formed into I aa aaoda each aa hy compression of powder particlee either oa a aahatrate |. or vithia a cavity. Alternatively, the aaodo ratal my he ia the fora of a cheat with the anode being coavolutoly «wad ia a jelly roll coafiguratioo together with tho coll eoparotor aad cathode. The sheet ratal ray also ha used, without wiadiag, ia a prismatic call. If dealrad, the aaoda ratal (particularly aiac) in amalgamated with rarcary after tha graia redactioo aad prior to placement of tha aaoda metal ia the call, la all tha aforementioned embodiments, with each extent of grain reduction there ia c concomitant redaction ia tha extent of graia boundaries aad a redactioa of gaaaiag at aach aitoa.
To farther reduce the extant of gaaaiag a email amount of a aarfaco active heterepolar anhataaco (sarfaetaat) of o typo that will net ae a hydrogen evolution inhibitor ia added to tha coll, lecraao of the heterepolar aatare of the earfoetrat it is generally at least slightly > soluble ia tha call electrolyte aad has a polar affinity to the aarfaco of the aaoda ratal particles with a coating being formed thereby, loch affinity ia perticalarly narked with respect to aiac particles caaraaly utilised ia aaodaa of alkaline electrolyte cclla. The surfactant may be effectively incorporated io tho coll ia varioae waya. For exaaple, it acy ha added to tha aaoda, iacorporated ia tha electrolyte, or ia the separator hy pre-wettiag or iapragaatiag the separator with the additive. Tha aurfactaat may avaa ho added to tho cathode. Ia all aach iaatucca the * aurfactaat migrates to the carface of the aaodo ratal particlee to form the requisite hydrogen gas inhibiting coating. Adding the aurfactaat to .¼ tho caodic material ia by direct addition to the powdered ratal (amalgamated ar uaemalgamatod) to form a aarfaco coating for the aaede "2octal. Alternatively, the aarfaetaat ia added to tha electrolyte which ia than adaixad with the sands aetal part idea with resultant migration of the anrfactant to the surface of the anode aetal particloa. Migration of the aur fee tent to the aaodo natal part idea nay alao ba effected by the addition of the surfactant te the separator or the cathode.
Alternatively, or ia addition, the anode notorial particles, andh aa sine, are prealloyad with a aaall aaoont of one or aero of iadioa, cadniua, gallioa, thallina, hiaanth, tin, and load ond then changed into particles with reduced anabor of grains or into individual discrete aiagla crystal particloa which are thereafter aaalgaaatod with aarcary.
Za order te affect redaction in tho anabor of grains, polycryatalliaa anode aoteriala eneh aa sine are heat treated at a tanparatnra below the welting point thereof for a sufficient tine whereby the nsaber of graias in the polycrystallino aaterial io rodaeod to one third or lose of tho original waterial.
Though ths anode notarial raaaiaa polycryatalliaa after thia heat treatweat, the aaosat of groin boundaries ore rodaced with tho redaction ia anabor of groina. Aa a raanlt, the aaosat of gassing in the call, with tha treated particloa, is aarhodly redweod since it ia tho area pf the groin bounderiea which is anat eoadeeiva to high choaicol activity and gas formation. In addition, aarcary infiltrates into grain boundaries readily. Vith the rednetioa of grain bouadariss there ia a redaction in the aaonnt of aerenry repaired for aaalgaaation with tha anode aaterial. With tha reduced grain anode aoteriala the aaonnt of aerenry repaired for aaalgaaation ean ha affectively reduced iron about 4-7X to np to about AZ. eat troataent of the aaeda aaterial ia depeadeadeat upon the fectore of purity of the polycryatalliaa starting aaterial, tha tenperature at which the heat traataaat is effected, and tha daration of anch heat treatment. It ia understood that hoot treataeat of powder particles of different hulk quantity aay differ in length of tine repaired since the interior af the aggregate ia seaewhet insulated hy anterior notorial and does not aae tho sane anoant of host as external aaterial in direct receipt of the heat. Za practice, a continuous taahling calciaod furnace «ill provide moot effective hmttag aid oe · remit , with properly designed eeleiaer, lees than tea minute· at teaweretaree above 370eC ie sufficient to effect eafficieat grala radacttaa. Seerystallisatioa ead grata coarsening depeade apoa nany factors each ee temperature, time, etreta energy withta the materiel, ead the parity. Ae a result, exact beet treatment parameter· ere determined ia accordance with tha specific beat treatmeat eqaipmat being atiliaad. For clarity, tho affective beat aad te^eratare, hcretaaftar referred to, relate to a direct application of heat to the material· Xa all avaata, a redaction of the aamber of gratae ta the material to oao third or loee of the original material ia the deairad remit· Tha beat treatment of the polyeryetalltae anode aaterial ia affective with both powdered material generally aaad ta tha conetraction of eo^preeead anode· ia cell· having a bobbin type structure, aad each treatment is also affective with respect to the treatment of metal atripa or aheeta atiliaad ta prismatic or convolutely wmnd call etraetaroe.
Tha parity of tho initial polyeryetalltae anode material determine·, ta part, tha length of time required to provide tha reqaicite redaction of gratae or eoavercely tho te^eratare at ahieh the aaterial ahmld he heated for a given period of time; the lower the parity, the higher the temperature or the longer the time period required· The moot common anode material for aloctrochoaieel eella ia nine with tha meat conmoa tapnrity contained therein being lead. Other, loee comma, anode materials include csdaiua, aickel, magnesian, aloaiaam, mengsneae, caleiam, copper, iron, lead, tia aad aixtaras thereof including mixture· with sine.
The alkaline electrolyte eolation ta «kick the anode material ia placed •ad which generally ia a factor ta tha g·· generation (usually theanode react· with the electrolyte with reeulteat gee formation) ie aaaally ca aqaeme eolation of a hydroxide of alkali or alkaline earth metal· each as KaOH and KO·. Common cathodes for the alkaline calls include mauganaee dioxide, cadmium oxide aad hydroxide, mercuric oxide, lead oxide, aickel oxide aad hydroxide, silver oxide aad air, Tha reduced grata number anodes of the present invention however are also of utility ta celle having other electrolytes ia which geeslag of the anode ie problenatical euch aa ia acid type electrolyte·.
Connen alkaline type eella centsla eenprosaed polyerystcUine aloe partidea having an average particle aiae of ahoet 100 wicroae. Bach ai each particles has ahoat 16 or nore gratae and ia accordance with the presact invention tha number of gratae ia each of tha particlea ia redacad hy heating the siac particlea at an affective teaperatare between ahoat 50 to 419.5*C (tha latter beiag tha amltiag point of aiac) for a miaiaaa period of tine ranging frets ahoat twa hoara at 50’C te sheet five niaetea at 419.5*C to redoes the anouat of grains to an average ef ahoat 3 to 5 grains par particle. Zinc partielaa having land iapnrities require a tanparatare of ahoat 100*C for the nlaiaan two hoar period to achieve a sinilar redaction in nanher of grains· Useful surfactants, which can ha added te the cell· ia accordance with the present invention in order to farther redaee the degree of gasalag, include ethylene oxide containing polymers each aa those having phosphate groups, saturated or uaeaturated woaocarboxylic acid with at leaat two athanelamida groupinga; tridecyloxypoly(othylenoxy) ethanol; and moat preferably organic phosphate eater·· the preferred organic phosphate eater· generally are aeneeater· or diestar· having the followiag fonsala: [so(ito) ] - r » o V <«)y where x ♦ y ® 3 M H, anmonia, aaiao, or aa alkali or alkalies earth natal K - phenyl or alkyl or alkylaryl ef 6-28 carbon atona Specific aaefnl organic phosphate eater anrfactaata include aateriala which can ha identified hy their cenmercial designation aa G494C 84600 (an anionic organic phosphate aster supplied hy 64F Carp, aa tha frat acid, baaed oa a linear primary alcohol, and being an tmaeatraliaed partial eater of phosphoric acid); 6494C 14810 (aa anionic complex organic phosphate eater supplied hy 64F Corp, aa tha free acid, having an aromatic hydrophobe, aad being an naaentralised partial eater of phosphoric acid); and KLB4V4C 44-040 (aa anionic nene anhatitntad ortho phosphate eater anpplied hy *489 Uyandette Corp).
It has been foaad that tha incorporation of a surfactant additive of tho typo referred to heroin in a coll in an amount of fro· 0.001Z to SZ, preferably t.MS to IX, and mat preferably 0.01 to O.SZ by might of the active anode componeet of the eoll, precludes or at least aigaifiCaatly Inhibits tha evolution of hydrogen within the cell, end thereby increase it· ehelf life end its aeefnl werh life.
The addition of the serfectaat to cells containing redneed nemher of anode netal grains or single crystal· ef cneb enode mtale provides a synergistic farther redaction of call gassing.
Though the nee ef single crystal anode materiel end the use ef organic IQ phosphate ester esrfacteate (08 Patent ies. 4,487,651 and 4,195,120 owned hy the asm assignee ea tha present invention) have separately hern known to effectively rednee cell gassing or to permit mm redaction of aerenry content in the anode without detrimatal increase ia gassing, the effect of the combisation baa aaoxpoctadly been discovered to ho considerably wore than additive. Thus, ia cells having anelgamtad single crystal cine anodes, the ament of mrenry in the amlgm can ha affectively reduced fron about 6-7Z to about 4Z or atatod differently tha rata of gassing af polycrystalline sine amalgam containing l.SZ mercery caa ha reduced hy about 2-fold with the use of single crystal sine, Similarly tha ntillastion of aa ergaaic phosphate eater surfactant each aa GAPAC RA600 with palycrystalliaa aiac amalgam anodes rcanltc ia about a 4-fold reduction of gassing with for txampla β.IX GAPAC 8A600. Bowever, ia accordance vith the present invention, a combination ef tho tm, i.n. a single crystal sine amalgam with e surfactant unexpectedly permits the effective reduction of tho mrenry to about l.SZ with about a 20-fold gassing rate inhibition er ohont doable whet night have haea expected. Ae a natter ef course, comblastion of chemical gaa reduction expedients dees not usually avm provide on additive effect nor decs excessive stilisation ef additives. The nee of the surfactant mterial with the redneed grain number sine anode mterial provides aa economical synergistic redaction of cell gassing te above that obtained with single crystal aaode asterial but mil below that obtained with tha high grain number polycrystalline sine.
The aiogle cry·tai· of slac ere preferably prepared oa described in eaid 08 Patent lo. 4,487,651, the diecloenre ol which is incorporated herein by reference thereto. Such procedure involves tbe font·tion of a thin ekin crucible on eaeh ef the line particles hy enidotioa in sir ot a tenperatere jaet below the netting paint (419*C) of the sine, heating of the akin enclosed line particle· ia on inert atawsphero above the waiting , , 1 point of the nine and alow cooling thereafter with removal of tbe onide ( skins. Zinc particle nines generally range between 80 and 600 micron· for i utility in eloctrochenienl eelle ond such method provides on effective sone for waking single crystal particles of ouch awall diwenaiona.
The Mount of wercury ia tbe eaede amalgam way mage fron 0 - 42 depending upon the eell utilisation ond the degree ef goaeiag to he tolerated.
The malgawated reduced grain aenber er single eryetal metal particles with awrfactaat additives sweh os CAPAC 14600 aro fornad into anode· for electrochemical cello particularly alkaline electrochemical cello.
Alternatively, tho oaodos oro forned fron the reduced grain nnnhor or single crystal swtal particles and tha surfactant migrates thereto fron other coll eopponents sneh oo tha electrolyte, separator or cathode to which tho snrfactaats have boon initially added. Other oaodo aetala capable ef being fornad into radnead grain aanber or single crystal powder· ond which ore woeful in electrochemical cello include 41, Cd, Ca, Co, Ph, Mg, Mi, and On. farther additional or alternative'expedient for reduction of gassing io tho alloying of polycrystalliae anode motel particle· with Indian or other additives prior to nwodo metal groin redaction or tho formation of tho oinglo cryotol motel partIdas, generally ia onoeato ranging between 25-5000 ppm and preferably between 100-1000 ppm. The omoont of mercury ia tho anode anolgaa nay range from 0 - 4X depending upon tha call <· utilinatioa and the degree af gassing to ho tolorntod. j "I The we IgM· ted single crystal metal particles with prealloy ad iaclnaioao of materiala inch oo indium aro then fonaod into aoodoa for olectrocboaieal cello partianlarly alkaliae alactraabanical cells. Other anode metal· capable ef being formed into aiagle crystal powders and which oro woeful ia electrochemical cells inclade Al, Cd, Ce, Cn, Ph, Mg, Hi, and Sa. Xt io naderoteod that with anodes of theeo motels tho proalloy material io not tho earns oo the anode active material hat ia laao .1 electrochenically active.
Ia order to more clearly illustrate tha affactivaaaoa of the present invention ia rodncing coll gaaaiag, tho following cooperative exaaple· are presented. Xt ia understood that oneb oxaaploa ore for illoatrativo purpose· only and that detail· contained therein orn not to he construed ee limitation· on tha prooont invention. Qaleaa otherwise indicated heroin and throughout the present opoeifieotion all ports aro ports hy weight.
XXAMPU 1 Throe batches of polycryotalliao sine of average particle aise ef about 100 micron· are hoot troatad for varying periodo of tine and tenperatures and are then analganated with about AS mercury by weight. A fourth hatch of AS mercury amalgamated polyerystalliae eiac ie set heat treated and ia need aa a central. TWa grama af eaeh hatch are placed ia 37S SOB aolutioaa (similar te the electrolyte ef alkaline cells) at 90*C with heating paranatara and gaaaiag rates given in Tabla 1: TAILS 1 Zinc Treatment ml gaa (2A hears) ml gaa (93 hour·) Control, not hooted 0.62 3.77 114 hour· at 400*C 0.25 2.07 235 hour· at 400*C 0.20 2.78 70 hoar· at A19*C 0.20 2.10 ,1n It ia evident fron the above that the hast treatment ef the present 30 invention eervea to more then halve the gaaaiag rate of amalgamated sine. Xt is farther evident that continued long tarn hooting does not significantly effect gaaaiag rotoa and ia generally economically nndtoiroblo.
RZAMTU 2 Polycryatalliaa aiac powder (average particle eiae ef 100 aicrama) froa the Rev Jersey Ziae Ce. (RJZ) ie heat treated at 370"C hy tumbling for one hour ia a rotating caleiae furnace. The powder, ae received froa Rew Jersey Ziae, hae the crystallise structure shown ia Tigers 1. After the heat trectaeat the powder has the eryatalliae etraetare ahewa ia Tigare 2 whareia graia sis· ia markedly iacreoaed, the Bomber of graiaa ia radaead aad the amount of grain bouadariea ia eoacomitaatly reduced. The polycryatalliae siac, aa received aad after heat treatmeat ia amalgamated vith 42 mercury aad two gram aaaplea ef each era tested for gaaaiag aa ia Rxaaple 1. Aa additional two gram sample ef 72 mercery amalgamated aiac from Royce Ziae Co., with similar polycryatalliae graia structure aad average particle aiaa, is also tasted for gaaaiag as aa additional control (representing prior art amalgamated aiac) vith gaaaiag results given ia Table 2: TABU 2 Ziae Type Oaseiag (ml) after 24 hears at 90*C As received from RJZ 42 Og 0.05 Heated et 370*C for 1 hoar 42 Bg 0.4 Rg Royce 0.25 Beat treatment, ae deecribed, provides aa aaode material having markedly aaparier gaaaiag properties when compared to untreated polycrystalline aiac •ad slightly worse than prior art amalgamated siac having considerably more mercury ia the amalgam.
BZANTU 3 r t, TWe grams ef each of the amalgamated siac materials af Raasplc 2 arc similarly tested for gaaaiag at 71 ®C after periods of 7 ead 14 days with the result· given ia Tables 3 and 4: TABU 3 Zinc Type As received from RJZ 42 Bg Heated at 370"C far 1 hoar 4X Rg 72 Rg Royeo Days (al gee) 14 days (al gaa) 0.98 1.95 0.50 1.19 0.44 0.05 TABU 4 ti Ziae Type As received from RJZ 42 Rg Rested at 370*C for 1 hoar 42 Rg 72 Rg Royce Oaaaiag Rate (al/garday) 0-7 Osya 7-14 days 0-14 day· 70 69 70 34 49 43 33 35 34 -9Both tho total smoaat of avolvsd gas and tha gassing rata of beat treated aiac powdera, after extended periods of tine, are coaparable to thoae of aiac powders aswlgaaatnd with significantly more Mercery.
It ia evident froa tha photomicrographs of Pignre 1 and 2 that the noaerona polycrystalline grain boundaries have been reduced ia number with a ceacoaitaat rednetioa in tho number of polycrystalline grains per particle without general ehaage in the shape of the iadividaal particles. The naaher of groina ia the hoot treated particloa ia a third or lass of that of tha original particles.
U4MPU 4 Zinc powder aaalgaaa containing 1.3Z mercury are made with standard grain polycryatalliaa aiac alone, atoadard groin polycryatalliaa aiac nith 0.1Z BA400 aa aa additive alaaant, aiagla crystal aiac, and single crystal aiac with 0.1Z K4400 ea aa additive elaaoat· Bpnal anounts of the aaalgaa powders are thaa placed ia equal anounts of 37X SOB alkaliae solution (typical electrolyte solution of alkaline calls) aad tasted fer gassing nt a tenperatare of 71*C. Tha O.IZ CAIAC B4400 ia added to tha alkaline aalntioa aad stirring of tha sine in anch solution roanlta in the deposition of tho surfactant on tha sine. Tha aaouat af gaaaing, aaasnrad ia nicrolitara/graa par day (aL/g-day) aad tha rata radnetioa factors (with the polycrystalline nine control being 1) ora ant forth ia Tabls 9: ABODE MATERIAL Polycryatalliaa sine, 1.9Z Hg Polycryatalliaa sine, 1.5Z Bg 0.1Z 14400 Single crystal sine, 1.5Z Bg Single crystal aiac, 1.9Z Bg 0.1Z B4400 A rate redaction factor (if aay) would ot aoat hove boon expected to ho shoot 7.8 (3.7 x 2.1) for o ceabiaed utilisation of aiaglo crystal aiac aad R4000 nith a gaaaing rata radnetioa to about 38 uL/g-day. Tha combination however synergistically reduces tho gaaaing to shoot double the expected rednetioa.
TABU 3 CASS1BC RATE BATS USDCTION FACTOR 295 1 eo 3.7 140 2.1 15 19.7 RXAMFU 5 Zinc powder smslgams of polyerystalliaa aad single crystal siac with sad without the 0.12 GAFAC BA600 additive are tested ·· ia Rxaaple 3 hat with 0.52 mercury saalgaae. The ameuat of gassing, measured ia microliters/gram per day (oL/g-dsy) aad tha rata reduction factors (with the polycryatalliae siac control being 1) are set forth ia Table 6: TABU 6 ABODI BATBUAL GA8S1BG RATS RATS RRDOCTXOI FACTOR Felycryetalliaa aiac, 0.52 Bg 720 1 Folycryatalliac siac, 0.52 Bg 0.12 RA400 130 5.5 Single crystal siac, 0.52 Bg 245 2.7 Single crystal siac, 0.52 flg 26 28 0.12 BA400 A rate roduetioa factor (if any) would at moat have bora expected te be shoot 14.9 (5,5 x 2.7) for a coahiaed utilisation of single crystal sine aad RA600 with a gaaaiag rata redactioa to about 48 uL/g-dsy. The combiaatioa however syaargistieally reduces tha gassing to nearly doable the expected redactioa.
It ia evident from the above examples aad tablas that tha single 20 crystal siac with one or more additives of tho preaeat iaveatioa ie markedly effective ia permitting large mercury reductions without iaereaee in cell gassing.
B2AHFU 6 Polycrystalline aiac ia prealloyed with 550 ppm af gallium aad 100 ppm of indium. 4 first sauple thereof ia then amalgamated with 1.52 mercury. A second sample ia made into individual single crystal alloy particles, aa described shove, prior to tha amalgamation with mercury. Two grams of each of the camples are placed ia a 372 KOH electrolyte eolation with gaaciag ct the ead of 24 aad 48 hours being measured at 90’C aa being representative of eorroeioa. Aa control aa amalgam ia mad· with polyeryetallino siac with 72 mercury similar to that comoaly used ia alkaline type cells. BeauIta of such teat· arc given ia Table 7.
II TABLB 7 8AM9U VOUSMB OP 0A8 (mL), 90· C 24 Boor· 40 Honra polycryatalliaa alloy 0.7 1.9 single crystal alloy 0.3 1.0 control (7X lg) 0.2 0.5 EUffU 7 A first portion of polyeryctalliao sine ponder ceataiaiag 0.04X lead ia amalgamatod with XX lg aad a second portion ia converted to iadividaal single Iq eryatal particlee prior to the amalgamatioa. The amalgams are then tasted far corrosion rata ia 1 It is evident that tha corrosion redaction of aaodo ratals aach as aiac hy the prealloyiag with corrosion rodaciag additive material· is greatly eabaaead hy tha formation of single eryatale fro· tho aaodo ratal-additivo alloy.
It ie aaderatood that the above exaaple· are illustrative ia aatare aad that changes ia material treatraat, material proportion·, the «pacific material·, coll coastractioa aad tha lika are within the acope of the praarat 2Q iavaatioa aa defined ia the following claim.
Claims (12)
1. A Method for making oa electrochemical cell, with reduced gaaaiog, with aoid coll having o polyeryatallino metal oaodo «object to goaoiag, said method eonprlaiag tho atopo of: a) rodncing the number of grains in said polyerystalliae metal to one third or leas of tho original number of grain*, b) forming eaid polycryatalline metal, with reduced number of grain·, into oa anode for eaid cells and c) placing said fornad polycry·tallin· natal anode into aaid coll.
2. The method of claia 1 wherein anid polycry·tailino metal ia heated at aa elevated temperature, below the molting point ol said motel, for a time sufficient to reduce the aanber of grains in aaid polycryatalline metal to one third or less, of the original number of grains.
3. The method of claim 2 wherein aaid polycryatailine metal ia selected from the group consisting of sine, cadmium, nickel, magnesium, aluminum, manganese, calcium, copper, iron, load, tin and mixture· thereof.
4. The method of claim 3 wherein said polycryatalline metal ia aiac and wherein aaid ainc ia boated at a temperature of between 50C to 419.5’C for a Minimum period of time ranging between five minute· and two bouro.
5. Tho Mthod of claim 1 wherein aoid amthod further comprises tho atop of adding a surface active hetero polar material additive having a polar affinity to aaid anode to aoid coll.
6. The method of claim 5 wherein aoid polycryatalline matai ia converted to single crystole.
7. The method ef claims 5 and 6 wherein sold aurfaco active hetero polar material additive conprise* aa organic phosphate eater having tha formula: [BO(BtO) 1 - P 0 n x <«), whore x ♦ y ” 3 M
8. , aaaoaia, amine, or aa alkali or alkaliae earth metal and k “ phenyl or alkyl or alkylaryl of 6-28 carbon atone. Θ. The method claimed in claim 7 wherein the 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 5 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. 1Q
9. The method of claim 8 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. 15
10. The method claimed in any of the preceding claims in which the 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 2o number of grains thereof.
11. The method claimed in claim 10 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.
12. A method of making an electrochemical cell, substantially as herein described with reference to the ( I 5 examples.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70083685A | 1985-02-12 | 1985-02-12 | |
| US06/749,688 US4632890A (en) | 1985-06-28 | 1985-06-28 | Anode metal treatment and use of said anode in cell |
| US06/764,454 US4585716A (en) | 1984-07-09 | 1985-08-12 | Cell corrosion reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE860198L IE860198L (en) | 1986-08-12 |
| IE57432B1 true IE57432B1 (en) | 1992-09-09 |
Family
ID=27418711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE198/86A IE57432B1 (en) | 1985-02-12 | 1986-01-23 | Cell corrosion reduction |
Country Status (16)
| Country | Link |
|---|---|
| AU (1) | AU594661B2 (en) |
| BE (1) | BE904216A (en) |
| BR (1) | BR8600570A (en) |
| CA (1) | CA1271217A (en) |
| CH (1) | CH671304A5 (en) |
| DE (1) | DE3603342A1 (en) |
| DK (1) | DK66886A (en) |
| ES (1) | ES8706854A1 (en) |
| FR (1) | FR2577351B1 (en) |
| GB (2) | GB2170946B (en) |
| IE (1) | IE57432B1 (en) |
| IT (1) | IT1204791B (en) |
| MX (1) | MX163835B (en) |
| NL (1) | NL8600347A (en) |
| NO (1) | NO169098C (en) |
| SE (1) | SE8600606L (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1267189A (en) * | 1985-06-28 | 1990-03-27 | Jerrold Winger | Alkaline cell employing a zinc electrode with reduced mercury additive |
| FR2634594B1 (en) * | 1988-07-25 | 1993-06-18 | Cipel Wonder | ELECTROCHEMICAL GENERATOR WITH ALKALINE ELECTROLYTE AND ZINC NEGATIVE ELECTRODE |
| EP0352604A1 (en) * | 1988-07-25 | 1990-01-31 | Cipel | Primary electrochemical generator with an alkaline electrolyte and a negative zinc electrode |
| DE3902650A1 (en) * | 1989-01-30 | 1990-08-02 | Varta Batterie | GALVANIC PRIME ELEMENT |
| CA2046148C (en) * | 1990-08-14 | 1997-01-07 | Dale R. Getz | Alkaline cells that are substantially free of mercury |
| US5626988A (en) * | 1994-05-06 | 1997-05-06 | Battery Technologies Inc. | Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture |
| CN101366135B (en) | 2006-06-28 | 2010-12-22 | 松下电器产业株式会社 | Alkaline dry battery |
| JP4516092B2 (en) * | 2007-05-10 | 2010-08-04 | パナソニック株式会社 | Alkaline battery |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE347906C (en) * | 1918-11-16 | 1922-01-25 | Alfred Eichhoff | Galvanic element |
| US2233578A (en) * | 1937-11-04 | 1941-03-04 | Western Cartridge Co | Method of making battery cans |
| US3623911A (en) * | 1969-03-03 | 1971-11-30 | Leesona Corp | High-rate consumable metal electrodes |
| US3853625A (en) * | 1970-04-03 | 1974-12-10 | Union Carbide Corp | Zinc fibers and needles and galvanic cell anodes made therefrom |
| BE789556A (en) * | 1971-10-01 | 1973-03-29 | Union Carbide Corp | ZINC BATTERY ALKAIN ELEMENT |
| CA1086988A (en) * | 1978-02-14 | 1980-10-07 | Maheswar Sahoo | Magnesium-lithium alloy |
| US4195120A (en) * | 1978-11-03 | 1980-03-25 | P. R. Mallory & Co. Inc. | Hydrogen evolution inhibitors for cells having zinc anodes |
| JPS56143662A (en) * | 1980-04-07 | 1981-11-09 | Tamagawa Kikai Kinzoku Kk | High strength zinc alloy for dry cell |
| EP0080064B1 (en) * | 1981-11-20 | 1986-07-30 | VARTA Batterie Aktiengesellschaft | Galvanic primary element with a negative electroless zinc-plated electrode collector |
| JPS58218760A (en) * | 1982-06-11 | 1983-12-20 | Toshiba Battery Co Ltd | Alkaline battery |
| DE3246957A1 (en) * | 1982-12-18 | 1984-06-20 | Varta Batterie Ag, 3000 Hannover | GALVANIC ELEMENT |
| JPS59186253A (en) * | 1983-04-01 | 1984-10-23 | インタ−ナショナル ビジネス マシ−ンズ コ−ポレ−ション | Electrode of battery |
| US4487651A (en) * | 1983-04-06 | 1984-12-11 | Duracell Inc. | Method for making irregular shaped single crystal particles and the use thereof in anodes for electrochemical cells |
| BR8503252A (en) * | 1984-07-09 | 1986-03-25 | Duracell Int | ELECTROCHEMICAL BATTERY, PROCESS FOR THE PRODUCTION OF AQUEOUS ELECTRICAL CHEMICAL BATTERY, AND COMPOSITION OF MATERIAL FOR USE IN THE PRODUCTION OF AQUEOUS ELECTROCHEMICAL BATTERY WITH REDUCED YEAST |
| JPS61131363A (en) * | 1984-11-28 | 1986-06-19 | Fuji Elelctrochem Co Ltd | Alkaline battery |
| JPS61131367A (en) * | 1984-11-30 | 1986-06-19 | Fuji Elelctrochem Co Ltd | Method of processing granular zinc alloy for alkaline battery |
| JPS61131366A (en) * | 1984-11-30 | 1986-06-19 | Fuji Elelctrochem Co Ltd | Method of processing granular zinc alloy for alkaline battery |
-
1986
- 1986-01-23 IE IE198/86A patent/IE57432B1/en unknown
- 1986-02-04 DE DE19863603342 patent/DE3603342A1/en not_active Withdrawn
- 1986-02-06 AU AU53248/86A patent/AU594661B2/en not_active Ceased
- 1986-02-07 BR BR8600570A patent/BR8600570A/en unknown
- 1986-02-10 ES ES551801A patent/ES8706854A1/en not_active Expired
- 1986-02-11 NO NO860475A patent/NO169098C/en unknown
- 1986-02-11 FR FR868601826A patent/FR2577351B1/en not_active Expired
- 1986-02-11 SE SE8600606A patent/SE8600606L/en not_active Application Discontinuation
- 1986-02-11 CH CH572/86A patent/CH671304A5/de not_active IP Right Cessation
- 1986-02-11 BE BE0/216257A patent/BE904216A/en not_active IP Right Cessation
- 1986-02-11 DK DK66886A patent/DK66886A/en not_active Application Discontinuation
- 1986-02-12 GB GB8603413A patent/GB2170946B/en not_active Expired
- 1986-02-12 NL NL8600347A patent/NL8600347A/en not_active Application Discontinuation
- 1986-02-12 MX MX1516A patent/MX163835B/en unknown
- 1986-02-12 CA CA000501694A patent/CA1271217A/en not_active Expired - Fee Related
- 1986-02-12 IT IT8619386A patent/IT1204791B/en active
- 1986-02-12 GB GB8802013A patent/GB2200791B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2200791A (en) | 1988-08-10 |
| GB8802013D0 (en) | 1988-02-24 |
| MX163835B (en) | 1992-06-25 |
| CH671304A5 (en) | 1989-08-15 |
| FR2577351A1 (en) | 1986-08-14 |
| GB8603413D0 (en) | 1986-03-19 |
| BR8600570A (en) | 1986-10-21 |
| NL8600347A (en) | 1986-09-01 |
| DE3603342A1 (en) | 1986-08-14 |
| IT1204791B (en) | 1989-03-10 |
| GB2200791B (en) | 1989-11-29 |
| AU594661B2 (en) | 1990-03-15 |
| ES551801A0 (en) | 1987-07-01 |
| ES8706854A1 (en) | 1987-07-01 |
| SE8600606L (en) | 1986-08-13 |
| FR2577351B1 (en) | 1989-09-29 |
| IE860198L (en) | 1986-08-12 |
| GB2170946A (en) | 1986-08-13 |
| NO169098B (en) | 1992-01-27 |
| CA1271217A (en) | 1990-07-03 |
| SE8600606D0 (en) | 1986-02-11 |
| DK66886D0 (en) | 1986-02-11 |
| GB2170946B (en) | 1989-11-22 |
| BE904216A (en) | 1986-05-29 |
| NO860475L (en) | 1986-08-13 |
| IT8619386A0 (en) | 1986-02-12 |
| NO169098C (en) | 1992-05-06 |
| DK66886A (en) | 1986-08-13 |
| AU5324886A (en) | 1986-08-21 |
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