see main article Battery
- 0678722: Reversible Galvanic Battery: edison us patent fist one metioned in wikipedia also appears to be on nicad not nickel iron)
- 0692507: Reversible Galvanic Battery: (edison, second one mentioned appears to be on nicad batteries not nickel iron)
- 0827297: Alkaline Battery: (edison)
- 1402751: Storage Battery Electrode and the Production of Same: (edison)
- 3622398: SEALED TYPE STORAGE BATTERY : points out the formation of h202 might be a problem leading to excess h2 and also exposure to electrolyte mist etc.though modern batteries seem to have overcome this
- 3630778: METHODS AND MEANS FOR RECOMBINING HYDROGEN AND OXYGEN IN A SEALED BATTERY AND CONTROLLING RECOMBINATION AT CATALYST SURFACES: Osmium and iridium might be cheaper
- 3650835: PREPARATION OF BATTERY PLATES WITH IRON OXIDES HAVING A FUSED COATING :
- 3785867: BATTERY PLATES COMPRISING A MULTIPLICITY OF PERFORATED METALLIC FOIL ELEMENTS AND A BATTERY UTILIZING SAME
- 3819413: RECHARGEABLE METAL ELECTRODE FOR STORAGE BATTERIES AND METAL-AIR CELLS: nother iron electrode
- 3836397: IRON ELECTRODE FOR ALKALINE CELLS: another one on iron electrode activated with sulfur etc not sure what the other parts were
- 3849198: IRON ELECTRODE PASTE FOR ALKALINE BATTERY PLATES
- 3853624: HIGH ENERGY DENSITY IRON-NICKEL:
- 3895961: Electrodeposition of iron active mass
- 3898098: Process for producing iron electrode: (electrodeposition method, says that electrodes used today (1975) are almost identical to those used by edison, says easy to deposit ferrous hydroxide, might be wrong hydroxide?)
- 3941614: Method of preparing high capacity nickel electrode powder
- 4016091: Method of preparing high capacity nickel electrode powder: says nickel coated steel wool is good
- 4029132: Method of preparing high capacity nickel electrode powder: again steel wool
- 4064331: Method for the preparation of iron electrodes: (iron electrodes for batteries; the patent on pyrolized resin and carbon black being used as the support matrix nickel plated screws)
- 4098964: Storage battery with recombination catalyst : catalyst info
- 4207383: Negative, highly active iron electrode: (iron electrode maybe not useful)
- 4335192: Method of preparing a sintered iron electrode:ammonium halogenides suitable for activating iron electrode
- 4374907: Gaseous hydrogen and oxygen combining and condensing device: preventing water on the catalyst surface
- 4383011: Multicell recombining lead-acid battery: redistribution of the water produced to ensure continuing electrolyte balance, the problem could be avoided by having the cells atmospheres independently sealed but that might be more expensive or harder, especially if catalytic combination is needed since a seperate combiner would be needed for each cell in the battery.
- 4399005: Method of nickel electrode production: (with zinc hydroxide)
- 4519425: Control method for loading battery electrodes: diffusion bonded steel wool? also mentions vacuum impregnation and hand pasted and centrifuge
- 4540476: Procedure for making nickel electrodes: a good one, forming nickel electrode straight on the electrode electrolytically looks like this could be transferred from a main electrode to the acceptor electrode in an electrode production tank too so you could form nickel electrodes from nickel ingot (need to check solubility of hydroxide)if you could get metal for some reason checked alibaba though and looks like it is more expensive substantially actually ,
- 4623600: Low shear nickel electrode: high stresses exist in the electrode applies to NiMH but check the molar volume change for nife might matter also streses caused by gas pressure
- 4663256: Nonsintered nickel electrode: another plastic emulsion type
- 4844999: Nickel electrode for alkaline battery and battery using said nickel electrode: porous electrode prob nihm
- 4908282: Recombinant battery and plate separator therefor :
- 5151162: Rechargeable storage battery with electroactive organic polymer electrodes in polar solvent electrolyte: electrically conductive polymers, maybe some of them would make sense as a conductinve substrate that's easy to make and low cost
- 5200282: Nickel electrode and alkaline battery using the same: (electrode rather than plates if wanted high disshcarge currents maybe) (nickel plate mesh, remove substrate)
- 5290640: Sealed rechargeable battery :
- 5506067: Rechargeable electrochemical cell and cell case therefor with vent for use in internal recombination of hydrogen and oxygen: takes the opposite approach, letting 02 into the cell to recombine excess h2 rather tahn lettign h2 out , maybe an osmotic membrane of Cellulose acetate could allow escape of excess water or equilibrium could be acheived soon enough as the chemical consumption of oxygen in the cell slows down . What about adding peroxide to the electrolyte during production to cause that equilibrium to be reached faster?
- 5788943: Battery-grade nickel hydroxide and method for its preparation:
- 6193871: Process of forming a nickel electrode (forming nickel electrode)
- 6254841: Recombination system for the catalytic recombination of hydrogen and oxygen, forming in storage batteries, into water:
- 6261720: Positive electrode active material for alkaline storage batteries: (have no idea if this is useful, something about a nickel hydroxide electrode in alkaline battery though I think this is probably be applicable to nickel metal hydride only ther eare many on nickel hydroxide electrodes)
- 6265112: Method of making a nickel fiber electrode for a nickel based battery system: another
- 6333123: Hydrogen recombination catalyst:
- 6492062: Primary alkaline battery including nickel oxyhydroxide: (nickel,zinc)
- 6500576: Hydrogen recombination catalyst:
- 6991875: Alkaline battery including nickel oxyhydroxide cathode and zinc anode: (another nickel zinc)
- 7081319: Preparation of nickel oxyhydroxide: (preparation of nickel oxyhydrozide with ozone suitable fo use n battery (ozone is easy to produce with high voltage electrodes))
- 7407521: Process for producing nickel oxyhydroxide by electrolytic oxidation: (process to produce nickel hydroxide maybe not useful though)
- 7435395: Alkaline cell with flat housing and nickel oxyhydroxide cathode: (another nickel zinc)
- 7691531: Alkaline primary battery including a spherical nickel oxyhydroxide: primary battery with nickel oxyhydroxide there seems to be no attempt make to contact the active material with a matrix but it is a high current discharge battery probably capable of more than 1C. read again maybe there are spherical particles, also the crystal structure might be a reason , also it expands after being added to battery apparently so that might be causing compressive stress if there are conductive particles too, could be a useful way to get the needed force
- : Recombiner system : catalyst Sealed battery doc describes way to make catalyst but takes a lot of platinum
patent 3583624, porous fiber matt described in such a way that surface arae can be calculated is okay at 0.5 C also describes a process used to load the electrodes that sounds like a lot of work, precipitating the iron in the electrode matrix, also says "electroprecipitation" can be used without elaborating.
http://www.freepatentsonline.com/4064331.html mentiones activating iron oxide by soakin in h2s water (h2s highly toxic note similar to cyanide but strong odor at subtoxic levels so relatively safe )also provides brand names for iron oxide might give an idea of purity freedom from various compounds required , is using pyrolized polymer and carbon as electrode maybe coudl use well heated pyrolized biomass instead of carbon and some other polymer or material for carbon but this seems to be only for small electrodes of 1.7 grams but may be used in conjuntion with other methods
- Swedesh pat.Nos 8.558/1897, 10.177/1899, 11.132/1899, 11.487/1899 and German Patent No.110.210 /1899.
- US.Pat No.678.722/1901, 692.507/1902 and German patent No 157.290/1901
- didn't look at http://www.patents.com/us-4330603.html
may be other patents, companies that make them and search freepatentsonline using the advanced search function for assignee name may turn up more and more recent
- http://www.freepatentsonline.com/3911094.html producing nickel oxydydroxide also discusses self discharg mechanisms of anode interesting but not needed might reduce self discharge rate
- [ii] Patent Number: 4,863,484  Date of Patent: Sep. 5, 1989
All (purportedly) of Edison's battery related patents, and it looks as though a large fraction of them relate to nickel iron directly or indirectly, from production of raw materials to the geometry of the electrodes. I started going through them but my computer is too slow. Most of them appear to be highly relevant; because he did not have high grade commodity materials to work with, this appears to be nearly an instruction book on making batteries from relatively low grade materials, although it might not be as good as a modern commercial one that remains to be seen, especially with a modest redesign combining the modern information above (and there is more like it I'm sure).
patent number 5,788,943 Aug. 4, 1998
http://www.freepatentsonline.com/4335192.html The classical method, dating back to Edison, for producing active metallic iron powder involves dissolving the pure iron in sulfuric acid, subjecting the iron sulphate derived from the solution to a baking process at 900° C., and reducing it in hydrogen current at 450° C. after washing and oxidizing drying. The iron powder so formed can subsequently be sintered either in the dry state or as a moist paste in an H 2 current after application to a support, and thus formed into an electrode. Later electrochemical processes for making active iron masses have also become known, e.g., in accordance with Austrian Pat. No. 320,770, which teaches the electrolysis of an iron nitrate solution, with copper salt added to it.
http://www.freepatentsonline.com/4443526.html nickel oxide electrode "A very suitable material is nickel coated steel wool." for current collector of cathode "As can be seen from FIG. 2, the cobalt containing electrode paste of this invention provides pasted electrodes which retain theoretical output of about 0.26 ampere-hours/gram for between 25 to 38 cycles, curves (A) and (B). Without cobalt additive, output drops to below 0.20 ampere-hours/gram of NiCO 3 ." But this is for a nickel oxide electrode. Note also that the efficiency with which the active material is used is very high, wonder if we can get this with oxyhydroxide
http://www.freepatentsonline.com/4236927.html High curretn hihgly active more on a sintered iron electrode Numerous attempts have already been undertaken to maintain the polarization within acceptable limits, for example, in that one mixes active iron material with nickel flitter (very fine nickel flakes) as conductive substance and stuffs this mixture into steel pockets or small steel pipes. This electrode type is very stable and sturdy; however, it can be operated only with small current strengths.[the pocket electrode edison used? need to check edison patents he may not have added the flitter or used adifferent metallic material for conductivity]
"A simultaneous cathodic separation of iron and of a conductive material such as, for example, nickel, entails a further improvement; " what does this mean?
another sugested option might be mixing pure iron powder with sodium chloride solution,sintering adnduring sintering the sodium chloride prevents the particles from sticking together so much as to reduce the surface area more than needed, then removing the excess chloride by dissolving it, read in previous patents that this can help with leectrode activation as well as mentioned it corrodes small pores in the surface of teh iron , also in the process when sinterin gis done in an atmosphere of H2 activates the electrodes (removes oxide I think although not quite sure yet what electrode activation altogether necessarilly entails). Even better use feric chloride then rather than dissovling it reduce it with hydrogen gas to form iron apparently works well, Note that this may not have been tested for lon gterm urability but they are in the know and do no expect it to be a problem and why patent something unless pretty sure it is useful unless they are just putting up fences in case it might be useful, also the patent said that "The theoretical capacity with respect to weight of an iron electrode lies at 960 ampere hours per kg (Ah/kg). In practice, once reaches capacities of about 200 to 250 Ah/kg because" this indicates that the cost calculations for the raw material amount of iron is much higher than the naive electrochemical equations, it migh tals obe comparable for the cathode reaction which would be bad but from descriptions for other electrode producing methods this might be wrong or out of date (filed 1978) check with that starved electrolyte nickel iron battery paper to see if can extract data on the actual performance vs. theoretical that they acheived
note the tendency to use diffusion bonding to connect fibers involved with fiber elecgtroe plaques, in many cases no tmentioned but may be important. Can probably calculate bulk specific resistance with and without bonding, contact resistance between 2 metals just touching not bonded can be found in references.
http://www.freepatentsonline.com/4250236.html says lithium hydroxide not needed "tubular electrodes"? "bonded iron plastic elctrodes"? Maybe an electrically conductive polymer would eb convenient maybe with metal fibers embedden in it "The positive electrodes were intentionally made with larger capacities than the negative electrodes" it shoudl be the other way around, otherwise you risk reacting the entire iron electrode during discharge and the iron usually provides some of it's own current collector matrix, maybe they made a mistake or maybe they did it on purpose for testing or something.
still doesn't explain how the variation in electrode geometry changees with charg/discharge cycles, but it seems that it is assumed that it stays more or less the same for some reason i.e. an electrode that has a high surface area to weight ratio when new will continue to have one, and without the need for additives or anything like that. Maybe the hydroxide precipitates out right after being formed and stays more or less put on the surface, and likewise does nto travel far during charging though ther must be some diffusion and maybe this is part of what limits battery life. Alternatively on in combination with this, maybe the processes during reformation of the electrode during chargnine are remarkable symmetrical with the ones during recharging, leading to a very slow reduction in surface roughness/porosity, or it usually goes up over time so as long as you start high engouh to be good you're okay.
Still need to identify the temperature dependent capacity loss mechanisms http://www.freepatentsonline.com/4132547.html another electrode one for the iron electrode, there are so many am skipping most of them, they can be found by searching easily http://www.freepatentsonline.com/6335120.html polymer support matrix , helps explain the method used to make the electrode in the sealed nickel battery testing doc, applies to both electrodes, why would you add syncrystallized materials they mention? could semimelting of the polymer work to provide adhesion thereby replace some of the ingredients here reducing ingredient count?
Performance/capacity loss mechanisms identified thus far:
http://www.freepatentsonline.com/4236927.html I think mentioned that the interfaces between the iron particles in a sinterd electrode can oxidize with some electrode production methods, increasing the resistance of the bulk of the electrod's current collecting matrix to high level,
Oxidization of the iron to iron oxide causes electrode passivation, the addition of something to provide sulfide ions in electrode or the electrolyte causes reductino of the pxide on an ongoing basis, but eventually the sulfide oxidises to sulfate and doesn't go back,
http://www.freepatentsonline.com/4250236.html says passivation occurs more so at *low* temperatures, not higher , also points out depletion of sulfide is one mechanism by which it is due to oxidization of sulfide to sulfate
The marketing material for e.g. nickel-iron-batteries.com indicates that there is a reaction that occurs which produces capacity loss with time and is more problematic at higher temperatures. This has not been identified yet and should be.
Activation of iron electrodes:
- http://www.freepatentsonline.com/4250236.html so sound like pretty much a mattery of getting and keeepinng oxides off and keeping them off
Battery-grade nickel hydroxide and method for its preparation B Aladjov - US Patent 5,788,943, 1998
patent 01488480 describes some failure modes and fix looks like ause for the waste glycerine from biodeisel too
- http://www.freepatentsonline.com/6335120.html (duplicate) Several types of electrode exist, in particular sintered electrodes and non-sintered nickel electrodes, also referred to as impasted or plasticized electrodes.
- http://www.freepatentsonline.com/4064331.html the patent on pyrolized resin and carbon black being used as the support matrix
nickel plated screws http://www.freepatentsonline.com/4663256.html anothe plastic emulsio n type one http://www.freepatentsonline.com/4540476.html a good one, forming nickel electrode straight on the electrode electrolytically looks like this could be transferred from a main electrode to the acceptor electrode in an electrode production tank too so you could form nickel electrodes from nickel ingot (need to check solubility of hydroxide)if you could get metal for some reason checked alibaba though and looks like it is more expensive substantially actually ,
- http://www.freepatentsonline.com/4462875.html electrodeposition electrochemical deposition also some further reading on it but is for catalyst might be not very suitable
- http://www.freepatentsonline.com/4337124.html nothe electrodep
check our foreign patents too sometime
- EP0889535 January, 1999 Nickel hydroxide active material for use in alkaline storage cell and manufacturing method of the same
- http://www.freepatentsonline.com/4000005.html electrode for nimh but still may be applicable here also some about vacuum impregnation of the slurry (not paste?
- might be able to use a microporous plastic filter pit fibermetal or paper against and then have the particles cake out on it a s afilter cake woud be limited though density
Options from patents (not all may be promising):
- http://www.freepatentsonline.com/4873157.html no catalyst needed
- http://www.freepatentsonline.com/4900642.html electrochemical recombination
- http://www.freepatentsonline.com/4952465.html particularly interesting, additive maybe suitable for nickel iron
- http://www.freepatentsonline.com/4908282.html mentions gas permeable film to let h2 out but not o2 and recombinant mat approach could be a bit cheaper than a mechanical vent
- remember that the above options had probably been tried by industry for nife cells and yet references indicate it was not until recently, with the use of combiner caps, that sealed nife batts became available, so they might not work as well in nife fro various reasons
- http://www.freepatentsonline.com/4629622.html more mat recombination
- http://www.freepatentsonline.com/4987041.html aux elect rode but in a different way
- http://www.freepatentsonline.com/6635387.html ammonium to reduce gas evolution in nickel iron batteries? the battery.
In French Patent No. 2,236,283 to Bonnaterre, http://www.freepatentsonline.com/5563004.html recombinant electrode in some other way General info on recombination and catalysts and how to make use of them practically:
- http://www.freepatentsonline.com/result.html?p=1&edit_alert=&srch=xprtsrch&query_txt=battery+recombine+hydrogen+oxygen+seal&uspat=on&date_range=all&stemming=on&sort=relevance&search=Search patent search for recombination