Revision as of 19:39, 18 July 2011

This page is deliberately somewhat free-form to allow an open exchange of ideas regarding the development, within an Open Source Ecology economy, of a Ni-Fe battery, a somewhat esoteric subject. The further down the page you go, the more free-form the information.

Products and Projects

Commercial Ni-Fe Suppliers

Iron Battery Wholesale Suppliers in the World

BeUtiltyFree: http://www.beutilityfree.com/Electric/Ni-Fe
Changhong: http://www.changhongbattery.com/Ni-Fe_battery_for_Solar_&_wind_appliances_pm53_m3.3_g47.html
Ironcore Power: http://www.ironcorepower.com.au/page3.php
Iron Edison: http://ironedison.com/
Zapp Works: http://www.zappworks.com/

Edison's Batteries

Anode

Cathode

Electrolyte

Cell Casing

Ed's Workshop

The Yahoo Group contains current efforts including a photo deck of his current battery. He also includes lots of other DIY projects that fit the theme here: DC motor control, Induction Furnace, Metal Casting, Electro-forming ...

Yahoo Group: http://tech.groups.yahoo.com/group/edsworkshp/
YouTube Channel: http://www.youtube.com/user/edsworkshop#p/u/14/CBGcdtAzzUE

Suggested Source:

Nickel Carbonate (Baily Pottery) approx $28/lb or less (depending on size of order)

http://www.baileypottery.com/clay/clays-chemicals.htm

Anode

Cathode

Electrolyte

Cell Casing

Other

noonco

Edison Battery Construction Nickel Iron‏ - YouTube: http://www.youtube.com/watch?v=K84PywMwjZg
Edison Battery Page: http://www.noonco.com/edison/

Source Materials

Nickel Compounds

Iron Compounds

Electrolytes

Notes

The parts added by me,Gregor, are only my personal notes, essentially unedited and may be indecipherable, but it was that or much less research would be here because I only had so much time to put in. In some cases parts will appear to mean nothing to people who are not already knowledgeable on the subject, or there may even be notes that only make sense in context of what I was thinking at the time. I am a believer in a high level of transparency, and I could have chosen to leave this on my hard drive instead, but I am more interested in success than avoiding embarrassment. I am no longer working on this project much due to management issues on the OSE project so if you want it cleaned up you will have to do it yourself.

Did some googling around and making notes, here is what I found, this is ordered chronologically and I will try to organize the information into sections later, but this is only a sampling of the information available. Sorry about the perforated boxes, I have not been able to stop the wiki from doing that, and the lack of hard returns is another wiki quirk:

apparently their efficiency goes *up* with time over about 2 years 80% as mentioned in the forum, purportedly unknown exactly why, would be nice to know.
from the manufacturer's of the modern batteries seems like efficiency is reasonably high actually, was not able to determine if the charging efficiency is nearly equal to the round trip efficiency, so the graphs might paint an overly rosy picture, but I think it is pretty close

http://www.changhongbatteries.com/Ni-Fe_battery_for_Solar_&_wind_appliances_p53_m2.2.1.html

low quality taken from browser history:

higher quality

http://www.nickel-iron-battery.com/
http://fieldlines.com/board/index.php?topic=144379.0 says "combiner caps" catalytic caps are available
http://sustainabledesignupdate.com/2010/02/green-battery-design/ says they have/had a team developing them
I emailed them http://apptechdesign.org/contact-us/ as asking for any documentation they can send on their work
http://www.solarpowerforum.net/forumVB/off-grid/4509-nickel-iron-batteries-8.html on one page here includes list of manufacturers that currently make them

the product pages etc form blog post http://www.uni-regensburg.de/Fakultaeten/nat_Fak_IV/Organische_Chemie/Didaktik/Keusch/chembox_edison-e.htm

more

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
http://edison.rutgers.edu/patents/01488481.PDF
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

May 19

I am making this a separate section because the wiki put a warning that the page may have been to long for some browsers to edit without breaking into categories.

Maybe look at the most specific or relevant patents and then search using the names of inventors etc.

The conductive scaffold for active material is referred to as a plaque of it is metallic (and maybe if not).

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.

electrodeposition method http://www.freepatentsonline.com/3898098.html says that electrodes used today (1975) are almost identical to those used by edison, says easy to deposit ferrous hydroxide, might be wrong hydroxide?

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

nickel iron cycle testing pdf has somethin gabout mucic acid to reduce the production of gas during charging that was from a pantent could probbaly find the patent

"Nickel hydroxide has been used for many years as an active electrode material for the positive electrode of alkaline batteries. The nickel hydroxide electrodes for these electrochemical cells traditionally fall into one of two major groups, sintered electrodes or pasted electrodes. Sintered electrodes are typically prepared by loading nickel hydroxide into a microporous substrate formed of a perforated steel sheet or mesh followed by sintering to form nickel oxyhydroxide, NiOOH.[why do the sintering if it is already loaded with nickel hydroxide??] The more recent pasted electrodes are prepared by producing an aqueous mixture of nickel hydroxide powder in a suitable carrier such as carboxymethyl cellulose. A porous metal substrate of fiber, foam or sponge is then impregnated with the solution to fill the pores of the substrate with nickel hydroxide. One advantage of the pasted nickel electrodes is the higher energy level approaching and even exceeding 600 mAh/cc compared to the typical energy density for sintered electrodes of about 400 mAh/cc. "

From the sealed nickel iron battery doc:

 Negative-limited Ni–Fe cells were assembled by stacking
 an iron electrode in between two sintered nickelpositive
 electrodes. The cells were housed in plexiglass
 containers in starved-electrolyte configuration, and were
 sealed with a plug containing 0.5 g of 2 at.% Pt/CeO2
 hydrogen–oxygen recombinant catalyst mixed with an
 equal amount of fumed silica. 6 V/1 Ah sealed, starvedelectrolyte
 Ni–Fe batteries were assembled in a plexiglass
 container comprising five compartments to

What? no Oxyhydroxide? When/how is it formed ?

maybe possible to form nickel hydroxide from metallic electrolytically, metallic nickel may be more expensive anyway though

faradaic efficiency of nickel iron cells, the sealed battery paper says is only 60% but again goes up over time to 80%

new docs

http://www.freepatentsonline.com/5989746.html listsa a few types of nickel electrode

searched "nickel iron batteries" on sciencedirect.com and went through the first 3 pages

http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TH1-4679T4B-1B&_user=10&_coverDate=08%2F31%2F1995&_alid=1757348188&_rdoc=2&_fmt=high&_orig=search&_origin=search&_zone=rslt_list_item&_cdi=5269&_sort=r&_st=13&_docanchor=&view=c&_ct=5535&_acct=C000050221&_version=1

&_urlVersion=0&_userid=10&md5=f94cc3c3f3988c1195112305e5e27202&searchtype=a

it employs electrodes with the pocket plate construction wherein the active material is encapsulated between double perforated folded steel strips. http://www.hblnicad.co.uk/Our%20Products.htm

note, these links are all broken, I have gone back and retrieved the titles of the papers and others, they are listed lower down http://www.freepatentsonline.com/5989746.html a pocket-type electrode, obtained by compressing electrochemically active material, in this case hydroxide Ni(OH) 2 , mixed with a conductor, into a metal pocket having perforated walls so that the electrolyte can impregnate the active material, but the active material cannot escape from the pocket; and

Maybe vacuum for gettin gpaste into the porous electrode, expose electrode to vacuum, cover in paste then expose to atmospheric, paste gets sucked into electrode , could also put electrode in a pan then vover with paste and maybe do one vacuum cycle

make a complete contained widget machine or glove box for electrode production to contain the (moderately) toxic materials if have to use paste

Cost of nickel oxide and hydroxide to determin if they might be cheaper than metal nickel in terms of the quantity of nickel:

Prices on the pages are FOB: free on board; assumption of responsibility by shipper for all costs until goods are placed on carrier , whatever carrier is, presumabbly the shipping company.

Ranges from 7 to 30$ on alibaba.com some grades migh tnot be suitable for batteris due to impurities, this can probably be determined from the information in the scientific articles and some manufacturer's conveniently say it is suitable for batteries. Detailed analysis may be available from suppliers. Samples may be obtainable form suppliers for prototyping with the specific material of concern. NiO2 (oxide) and Ni2O3 (peroxide) or NiO see wikipedia for CAS numbers but the pages sometimes fail to distinguish saying oxide always? http://en.wikipedia.org/wiki/Dictionary_of_chemical_formulas/Merge/N note that chemical suppliers are sometimes very sloppy about talking about chemicals and chemical names and may make mistakes, a lot of chemists are, with oxide meaning any of the oxides so need to double check the exact chemical used in the patents if the route of producing nickel oxyhydroxide from nickel oxide by oxidization in o2 gas, ozone in solution or humid ozone gas or otherwise, is chosen.

Details on which impurities are problematic needs to be tracked down so the cheapest stuff that will do can be used. Testing works to some degree but not if the impurity causes reduced life which would go undetected. Nickel hydroxide I did not check yet because I still need to look at other patents and see if electrode can be made straight from it.

alibaba, jus tsearch nickel oxide or "nickel oxide" battery

conclusion: In terms of nickel content, depends on who it is purchased from etc. But it is usually substantially cheaper than nickel metal.

The if vacuum is use for pasted equivalent electrode, battery could be designed such that the pasting process occurs inside the battery maybe no point though, but trying to keep the reactions and toxic materials in the battery during manufacture rateher than needing to pour and transfer them would be nice , and using nickel metal as a starter material coudl be a perk in that regard actually nickel oxide not soluble in water is it? No do not accept "insoluble" as an answer, want to know exactly how soluble

Is apparent that the reaction products stay put where the reaction material was before, unlike in a lead acid battery where they form a sludge of material at the bottom of the battery, that assumption tripped me up for a bit there so be it known.

http://academic.research.microsoft.com/Paper/11920038 solubility of NiO

maybe post on amateur chemist forums when the time comes ask for help clearin up uncertainties, maybe experimenting like finding solubility of nickel oxyhydroxide or p

 iron air battery sounds interesing http://www.freepatentsonline.com/4474862.html wonder what the efficiency for rechargnin is probably very low, could make a good electrid lifetrack

http://www.freepatentsonline.com/4335192.html ammonium halogenides suitable for activatin iron elecrtrode

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.

http://www.freepatentsonline.com/4250236.html

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
http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B9D09-4XS7F7F-1Y&_user=10&_coverDate=06%2F15%2F2010&_alid=1757708553&_rdoc=4&_fmt=high&_orig=search&_origin=search&_zone=rslt_list_item&_cdi=62089&_sort=r&_st=13&_docanchor=&view=c&_ct=2063&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=8cc228681b8c7fe749c54ac6ede1fad4&searchtype=a might be duplicate
http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TH1-3VR6J5Y-2&_user=10&_coverDate=09%2F30%2F1996&_alid=1757708553&_rdoc=1&_fmt=high&_orig=search&_origin=search&_zone=rslt_list_item&_cdi=5269&_sort=r&_st=13&_docanchor=&view=c&_ct=2063&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=9d946a5af21722601c868ded3c95c8ed&searchtype=a might be duplicate

There are a great number of patents on electrodes, a lot to learn here for the background and a lot of good ideas. Apparently searching for nickel iron battery patents turns up very little but there are a huge number of good and valuable patents on the constituent parts and electrolyte which can be found with the appropriate search terms incorporating some knowledge of how the batteries work.

http://www.freepatentsonline.com/result.html?p=1&edit_alert=&srch=xprtsrch&query_txt=Iron+sintered+electrode+battery&uspat=on&date_range=all&stemming=on&sort=relevance&search=Search

No doubt this applies to searches in other venues as well like on sciencedirect etc.

While at first it appears there is relatively little info on these batteries there is a vast amount just under the surface that can be mined out and is fairly informative. Clearly after the information is mined out of the public spaces there will still be plenty left squirreled away by companies for one reason or another that is just not available to us. Some of this will need to be re figured out on paper by someone with some chemistry knowledge/ rediscovered though prototyping/testing/research.

aluminum air if coudl use aluminum elecrdodes from clay wonder how to make the gas permeable electrode though maybe coudl metallize a gas permable polymer layer with vacuum vapor deposition or similar or could maye the polymer slighlyt conductive and embed metallic fibers or similar

check out other ways to make active iron electrodes are probably lots of them, includes a low solubility sulfide mixed in the iron or added in excess to the electrolyte, adding sulfide to the iron electrode, other ways of getting sulfite where it needs to be, apparently present as an impurity in adequate amount in some iron anyway so thats handy.

nickel zinc might be worth lookin g into since they have higher cahrge/discharge efficiency are more efficient

http://edison.rutgers.edu/battpats.htm patent 01488480 describes some failure modes and fix looks like ause for the waste glycerine from biodeisel too

searchable archive of the pdfs which I ocred, I tried to upload this to the wiki but it is more than 7 megs and not a permitted file type (.zip) not can batch uploading of PDFs be done, so maybe someone else can put this information on the wiki where it will not disappear in the future as it will on zippyshare, but will rather remain conveniently searchable for future developers: http://www30.zippyshare.com/v/76183680/file.html

why is it that edison keeps mentioning that sulfur is undesirable in the vulcanized rubber in the insulators but in modern batteries is is used to acitvate the electrode?

yet another optio nfo the anode is to take copper crystals and iron particles and compress them into a blockL 2683182 says low purity iron can be used for this

http://www.freepatentsonline.com/5151162.html electrically conductive polymers, maybe some of them would make sense as a conductinve substrate that's easy to make and low cost
http://www.freepatentsonline.com/3836397.htm another one on iron electrode activated with sulfur etc not sure what the other parts were
http://www.freepatentsonline.com/3819413.html nother iron electrode
http://www.freepatentsonline.com/4844999.html porous electrode prob nihm
http://www.freepatentsonline.com/6265112.html another
http://www.freepatentsonline.com/7691531.html 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
http://www.freepatentsonline.com/6265112.html another for fibrous electrode looks relatively useless for us
http://www.freepatentsonline.com/4623600.html high stresses exist in the electrode applies to NiMH but check the molar volume change for nife might matter also streses caused buy gas pressure
http://www.freepatentsonline.com/4016091.html says nickel coated steel wool is good
http://www.freepatentsonline.com/4029132.html again steel wool
http://www.freepatentsonline.com/3849198.html
http://www.freepatentsonline.com/3941614.html
http://www.freepatentsonline.com/3849198.html
http://www.patents.com/us-4519425.html diffusion bonded steel wool? also mentions vacuum impregnation and hand pasted and centrifuge

How hard would it be to make the nickel cloth again? if diffusion bonding is needed then that reduces the benefit of using steel wool and cloth can't release inhalable fibers when you dont want it to , maybe sintering not so bad either would be durable too , oh it nickel plating of the wool happens after diffusion bonding it says maybe beat or vacuum clean or blast with high pressure air the steel wool to reduce the amount of small fibers involved to reduce amount of stuff that migh tbe released subsequently maybe no point nickel metal anyway http://www.nmfrc.org/epadocs/1994f.htm on chemicall yplating steel wool

maybe nickel foil but without compression no probably not need the metal scaffold to be condictive throughout maybe a method could be developed to use salt or sugar and get the nickel foil bit sto bond with electrochemical plate-out

maybe plate-out on the active material or a polymer matrix?

check the polymer paste methods again maybe flouropolymer not needed coudl use a different material combo they mention also they explain why they use fluoropolymer, highly hydrophobic, maybe a substitute can be found.

also check the conductive pyrolyzed plastic again check conductivit of activated carbon etc to see conductivity of pyrolized biomass

http://acs.omnibooksonline.com/data/papers/1997_ii454.pdf looks very high 30 ohm/cm vs 6.9 microohm per cm for nickel, if the plaque is 10% dense specific resistivity of the resulting matrix material pretty high 300 ohm/cm maybe it is a lot lower with pyrolized polymers
http://webcache.googleusercontent.com/search?q=cache:VngbRXiriPcJ:acs.omnibooksonline.com/data/papers/2004_E060.pdf+http://acs.omnibooksonline.com/data/papers/2004_E060.pdf&hl=en&gl=ca says 1.99177x10-3 δ /cm which is plenty low esp if combine switha central nickel rod or nickel wire

that US3853624.pdf file gives an idea of the sort of fiber density and size that is suitable for electrodes

Maybe thixotropic material to prevent escape, have a look at gells again do the diffuse and sort of spread throughout a liwuid they are immersed in or stay solid maybe the nickel plating process would electrically attach the wool together appropriately

wool needs to be cleaned adequately first

with the iron electrode make it from scratch What to do about the need to obtain nickel from environment in abundance?

if do buy stuff needs to be commodity as possible so no buyin nickel wool or electroplate stuff then

That leaves the polymer maybe dense polymer fibers woudl work

bickel plated bolts for final termination, and probably a bit more fragile (though actually carbon fiber is pretty tough) so might want to make the branching of the fiber stuff heirarchical if can maybe test it for wtrenght first also extra dense can be done easily also support it in the casing of the battery with foam supports to distribute loads due to shock etc and make it a block instead of a plate maybe check the tensile strength of pyrolized plastics of varying sorts esp common and cheap ones remember carbon fiber is made by pyrolizing aramid right and we can make polyaramid 11 or whatever see wikipedia under biopolymers

need to find the patents that mentioned downsides of including carbon or graphite in the electrodes on either side

block can have veritcal and horizontal holes etc. easily to allow gas to excape s

for heirarchy could use fiber and powder together need to have contingency pland in case a certain commodity no longer available hardly, also need co calculate costs as go along they have to be less than commercial batteries, if as mentioned above only a quarter of the active electrode on iron side actually gets used (also tells how much material need to sinter to make the electrode), also on the nickel side need to know what fraction of active material gets used

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.

maybe rods would be useful if nickel mulit strand wire is avilable or something

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

"Eagle Pitcher Ni " is a commercial plaque sutiable fo rht enickel side

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 ,

damn, went back to look at some of the scientific articles and the urls are all broken and cant be fixed. no correlation between url and articles at all .search browser history to find the title and put them with the urls so can find the articles again

scrap nickel prices? with electrolytic loading maybe particularly easy to use scrap metal though of course it can be used anyway in one way or another.

find what fraction of nickel can expect to be actually used for a battery like with iroon eectrode compare for different electrode types esp edison and nickel plated steel wool, in the scientific docs that describe construction of cell this would be revealed, maybe in some patents too, remember seeing the information on weight and amp hour capacity of a pocket electrode by edison in his patents, need to look it up again, the efficiency will probably be a lot higher for a pasted electrode.

bulk conductivity of steel wool at large medium and small scales

Okay my browser malfunctioned when I was searching for the names of the articles from my history and wiped out the history. So I search again for the best ones and started copying the titles downWe basically want all of them that mention nickel iron specifically and most of the others that relate to eletrodes made from nickel oxyhydroxide, and metallic iron and/or iron oxides. The electrode ones may not mention "nickel iron" per se because e.g. a good iron electrode in nickel iron battery can also be used in many other battery chemistries.

searched "nickel-iron" battery went through to end of second page

"nickel-iron" storage cell searched first page only one up at the top
"nickel/iron" battery searche dto the end of second page
Nickel iron battery need to record searched to the end of the 3rd page page
Nickel iron electrode record went through thr first 2 pages migh tbe more
also can look at the related papers section

Assessment of performance characteristics of the nickelnext term---previous termiron cellnext term

Self-discharge of Fe–Ni alkaline batteriesnext term

The role of FeS and (NH4)2CO3 additives on the pressed type Fe electrodenext term

The electrochemical properties of Fe2O3-loaded carbon electrodesnext term for previous termironnext term–air previous termbatterynext term anodes

Effect of metal-sulfide additives on electrochemical properties of nano-sized Fe2O3-loaded carbon for Fe/air batterynext term anodes

Passivation of ironnext term in alkaline carbonate solutions

Electrochemical characteristics of ironnext term carbide as an active material in alkaline previous termbatteriesnext term

Temperature limitations of primary and secondary alkaline battery electrodesnext term

97/03847 Performance characterization of sintered ironnext term electrodes in previous termnickel/ironnext term alkaline previous termbatteriesnext term

SECONDARY BATTERIES - NICKEL SYSTEMS Electrodes: Nickel

Assessment of performance characteristics of the nickelnext term---previous termironnext term cell

Nickelnext term-based rechargeable previous termbatteriesnext term

Developmental studies on porous iron electrodesnext term for the previous termnickel---ironnext term cell Performance characterization of sintered ironnext term electrodes in previous term nickel/ironnext term alkaline previous termbatteriesnext term

On the key importance of homogeneity in the electrochemical performance of industrial positive active materials in nickel batteriesnext term Electrochemical behaviour of Teflon-bonded ironnext term oxide previous termelectrodesnext term in alkaline solutions Rechargeable alkaline iron electrodesnext term high curent though Performance characterization of sintered ironnext term electrodes in previous termnickel/ironnext term alkaline previous termbatteriesnext term

The role of lithium in preventing the detrimental effect of ironnext term on alkaline previous termbattery nickelnext term hydroxide electrode: A mechanistic aspect looks like not just about nihm may be some applicable to nife too Role of activation on the performance of the ironnext term negative previous termelectrodenext term in previous termnickel/ironnext term cells Rechargeable alkaline iron electrodes

Microstructure changes to ironnext term nanoparticles during discharge/charge cycles The discharge capacity of the first cycle was extremely high, 510 mAh/g-Fe, at a current density of 200 mA/g-Fe, check what that is well, it;s 510 Ah per Kg as compared with the ~250 figures in the patents for sintered electrodes with reduced salts on their surfaces (a high rate one) and 960

Really interesting looking :\

Assessment of performance characteristics of the nickelnext term---previous termironnext term cell

SECONDARY BATTERIES - NICKEL SYSTEMS Nickel–Iron
SECONDARY BATTERIES - NICKEL SYSTEMS
SECONDARY BATTERIES - NICKEL SYSTEMS Electrodes: Iron

The nickel/ironnext term battery

A nickel-iron batterynext term with roll-compacted previous termironnext term electrodes

Less interesting:

The role of lithium in preventing the detrimental effect of ironnext term on alkaline previous termbattery nickelnext term hydroxide electrode: A mechanistic aspect

Iron/next termcarbon-black composite nanoparticles as an previous termironnext term electrode material in a paste type rechargeable alkaline previous termbatterynext term

Research, development and demonstration of a nickel—iron batterynext term for electric vehicle propulsion there are several papers with this term LO

Microfibrous nickelnext term substrates and electrodes for previous termbatterynext term system applications can't use them anyway most likely though maybe The fabricated previous termnickelnext term electrodes that included a supporting previous termnickelnext term mesh in the substrate tested in a 26% KOH half-cell delivered a specific capacity of more than 250 mAh/g of the electrode weight (i.e. fibrous substrate, previous termnickelnext term mesh, and active material) at a 1.0 C discharge rate. An Auburn electrode without a previous termnickelnext term mesh tested in the same half-cell attained a higher specific capacity of 268 mAh/g at a 1.37 C discharge rate. The substrates used in these electrodes had porosities of 95–97%, and greatly improved the specific capacity of the previous termnickelnext term electrode. With the use of the previous termmicrofibrousnext term electrode, improved specific energies of previous termnickelnext term-based cell and previous termbatterynext term designs are possible. When assembled in a previous termnickelnext term–hydrogen (Ni–H2) boilerplate cell, the specific capacity of nearly 230 mAh/g was observed for the previous termnickelnext term electrode at a 0.5 C rate during the 127th cycle test.

Assessment of performance characteristics of the nickelnext term---previous termironnext term cell
The electrochemical generation of ferrate at pressed ironnext term powder previous termelectrode:next term comparison with a foil previous termelectrodenext term
The role of FeS and (NH4)2CO3 additives on the pressed type Fe electrodenext term
Alkaline poly(ethylene oxide) solid polymer electrolytes. Application to nickelnext term secondary previous termbatteriesnext term

least interesting

Importance of alkaline accumulators in the application of renewable resources , can tell something about the needed performance reqs

Alkaline Battery Separators

The role of halide ions on the electrochemical behaviour of ironnext term in alkali solutions
Nickelnext term-based rechargeable previous termbatteriesnext term
maybe or clearly probably only applicable to nihm but didn't want to loose
Effect of zinc and ironnext term ions on the electrochemistry of previous termnickelnext term oxide previous termelectrode:next term slow cyclic voltammetry
An electrochemically impregnated sintered-nickel electrodenext term An electrochemically impregnated sintered-previous termnickelnext term porous previous termelectrodenext term with a capacity of 225 ± 10 mAh per g of active material has been developed nihm, can calculate from wikipedia how much that is relative totheoretical also in one of the above it was mentioned the overall weight of the electrode for a fibrous electrode vs. current per gram, could make asumptions actually said it was 97 oercent porous so that tells how much but migth be weightin the water too still puts a lower boundary
Electrocatalysis of anodic oxygen evolution at the nickelnext term hydroxide previous termelectrodenext term by ferric hydroxo species in alkaline electrolytes
The significance of electrochemical impedance spectra recorded during active oxygen evolution for oxide covered Ni, Co and Fe electrodesnext term in alkaline solution
The influences of some additives on electrochemical behaviour of nickel electrodesnext term
The role of lithium in preventing the detrimental effect of ironnext term on alkaline battery previous termnickelnext term hydroxide previous termelectrode:next term A mechanistic aspect
The effect of lithium in preventing ironnext term poisoning in the previous termnickelnext term hydroxide previous termelectrodenext term

may 21

http://www.freepatentsonline.com/5989746.html A nickel electrode of the pasted type is made by depositing a paste either on a two-dimensional conductive support such as expanded metal, a grid, a fabric, a solid strip, or a perforated strip, or else in a three-dimensional conductive support that is porous such as a felt, a metal foam, or a carbon foam. so carbon okay prob at nickel electrode though saw another one that mentioned it had significant downsides

a polymer cloth pocket could be used to keep the paste in, maybe this was partly what the pocket used in the sealed battery doc was for doubt it because had elastomer binde r
Document EP-0 658 948 describes an Ni--MH alkaline storage cell provided with a positive electrode of the pasted nickel electrode type constituted by nickel hydroxide, as its active material, and by graphite, as its conductor. The nickel positive electrode provides the storage cell with increased stability at high temperatures of use. Furthermore, it can be seen that the nickel positive electrode cannot be associated with a cadmium negative electrode, because, in that case, the graphite oxidizes into carbonate ions which pass into the electrolyte.
To increase the rapid discharge performance of a non-sintered nickel electrode, document JP-57 138 776 proposes a conductor constituted by a mixture of particles, preferably of graphite powder, and of fibers made of carbon or of stainless steel, for example. stainless steel okay?

purpose of cobalt additives mmight be to increase conductivivty

During the first charge of an alkaline storage cell provided with a nickel electrode containing a cobalt compound as its conductor, said compound is oxidized into cobalt oxyhydroxide CoOOH in which the cobalt is brought to oxidation number +3. The cobalt oxyhydroxide is stable in the normal operating range of the nickel positive elec
ask chemist if there is a conductive polymer that would be okay for the nickel (resistant to redox environment) and if it is expensive or coudl be synthesised by makers
there was on that mentioned that nichrome wire or mesh could be used migh tbe more available thatn nickel
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
JP0378965
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

maybe putting the electrodes horizontally could be better to prevent loss of paste for one of the electrodes if wanted to eliminate binders and density an fibrosity of fiber mat was relatively low (like steel wool?), could then have either other electrode horx too with tray spearating it from the other one and conduction occuring aroud edges of tray also coudl have cloth barrier or something tightly woven to reduce escape of particles during mecahnica lagitation, or have electrolyte ffairly viscous with an additive, probably not much of a problem thoug heven if particle sget fro, one electrode to the other they would just stay there in the discharged state, main thing is to keep active material close to the current collector, also could be adjacent then stack for battery, check what effective the resistance of the electrolyte is, might be too high for this to be practical (ionic current of the relevant ions vs/ voltage). If a bed of fibrous nonwoven cloth material like tyvek or what is used often in depth filters for water filters, which is a effective particle barrier at the particle sizes concerned, but also a high porosity for ionic current, could form the bottom of the tray

in terms of shape changes of active material particles or mass that one with the nanoparticles had evidence of it changing but aparently happens quite little as was not a problem for even them causeing relatively little variation in particle size and total surface area thoug hit was growth in particle size/reduction in active area. wait, that migh thave been a nickel hydride cell double check, but in any case this is the assumption; very little change in particle or surface geometry occurs, though some does and this is taken advantage sometimes to electrolytically attach the particles together and to the current collector surface for better conductivity, also particles that are not attached such that electron current flow can practically occur are not utilized as active mass (they are wasted) so it's important to have them connected in this way. In edison cells a significant fraction is wasted, need to check again how much, can comput form wieght of the tubes etc.

should eventual;y preserve the research page by spidering to prevent link death being a problem, then upload the finished webpage with files maybe 3 deep for links so get pdf files for posterity since development will continue and also for repair manuals writing etc.

more docs:

google scholar'd "nickel-iron" battery electrode and went through the first 100 hits:
Journal of Materials Science Letters Volume 12, Number 9, 620-622, DOI: 10.1007/BF00465571 Electrochemical impregnation of the nickel hydroxide electrode under ultrasonic irradiation A. Chiba, T. Tani and Y. Ouchi
Electrocatalysis of anodic oxygen evolution at the nickel hydroxide electrode by ferric hydroxo species in alkaline electrolytes hi
Comparative Study of Fe2O3-Nanoloaded Carbon and Fe2O3-Nano/Carbon Mixed Composites for Iron-Air Battery Anodes
Electrochem. Solid-State Lett., Volume 8, Issue 9, pp. A476-A480 (2005) LO
6V, 60Ah nickel-iron battery.
Bulletin of Electrochemistry. Vol. 6, no. 2, pp. 263-265. 1990
High reversibility of the charge discharge reaction leads to the longest service life. The iron electrode has low hydrogen overvoltage. Its ionisation potential and hydrogen evolution potential are very close in alkaline medium. As a result, the self discharge of this system is 1-2% of the nominal capacity at 300K (1). The advanced Ni/Fe batteries with an energy density of 55-82 Wh/kg (2,3) serve as power sources for electric vehicles. The electrode fabrication techniques and the performance characteristics of the 6V, 60 Ah Ni/Fe battery are presented in this paper. * Very HI

Open-circuit potential—time transients of alkaline porous iron electrodes at various states-of-charge
Purchase
$ 31.50
Solid-State and Structural Chemistry Unit, and Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore-560 012, India iron air mostly LO

Effect of synthesis conditions on characteristics of the precursor material used in NiO·OH/Ni(OH)2 electrodes of alkaline batteries LO

Mechanisms of self-discharge of the negative of alkaline accumulators available as html without images through google's view as html, google title and there it is

   "The self-discharge of the negative in nickel-iron batteries is caused mainly by the
   anaerobic attack of the active material by water. As in other instances of corrosion,
   this process can be retarded by cathodic protection. A cadmium negative is practically
   immune against water, but in an incompletely sealed"
   It is known that the negative in alkaline nickel accumulators loses charge on
   standing idle, the loss being of the order of 20 % per month in Ni-Fe cells 1
   and 2-3 % per month in recent makes of Ni-Cd cells.2 In contrast to the lead-
   acid battery, no attention has yet been given to the corrosive mechanism causing
   self-discharge in the alkaline storage cell. 
   In  1955 thogugh porous nickel plate (6-3 cm x 1.7 cm x 0.3 cni) made from low-density carbonyl powder
   by sintering in H2 at 950” C without compression. The pore volume of the plate was
   85 % and the surface area was l-l*mz/g, as measured by the B.E.T. method. In one
   spiral and the negative. With a
   70-cm nickel strip, the rate of self-discharge was about 1000 times as fast as in the absence
   of a water-line. This effect was also found in commercial Ni-Fe cells, the water-line
   being present round the rod supporting the negative. On separating the latter from the
   rod, and inserting a meter, an air junction current of 0.3-0-4
   mA (in a 10 A h cell) was measurable. This current is large enough to account for t[sic] so nickel electrode needs to be submersed

also indicates that maybe id we pressurized the battery self discharge could be reduced but pressure might eb too high Also explains the main problem by far with self discharge in nife is that the iron reacts with the water

High energy density micro-fiber based nickel electrode for aerospace batteries LO

An iron—air vehicle battery

http://books.google.ca/books?hl=en&lr=&id=_PGzaO48Rz0C&oi=fnd&pg=PR4&dq=%22nickel-iron%22+battery+electrode&ots=WUrahYuzAm&sig=QjxT0uYcDvtejauBT0ClpFO9XZs#v=onepage&q=%22nickel-iron%22%20battery%20electrode&f=false

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Electrochem. Solid-State Lett. / Volume 4 / Issue 3 / BATTERIES AND ENERGY CONVERSION

Ceria-Supported Platinum as Hydrogen-Oxygen Recombinant Catalyst for Sealed Lead-Acid Batteries

Electrochem. Solid-State Lett., Volume 4, Issue 3, pp. A23-A26 (2001)

The influences of some additives on electrochemical behaviour of nickel electrodes might be interesting not clear

The effect of iron hydroxide on nickelous hydroxide electrodes with emphasis on the oxygen evolution reactionstar, open might be interesting since some particles will get in the nickel leectrode and eventually mix

Sealing the battery

The need to add water to an unsealed cell is a substantial problem with NiFe batteries because they convert a particularly large amount of water to H2 an O2 no mattery how well they are treated.

The hydrogen and oxygen produced can be catalyticaly recombined with so-called catalytic combiner caps, which are available for lead acid batteries and also specifically for nickel iron although they may be the same. The sealed battery document details a method of making catalytic material. It is usually a platinum catalyst with significant amounts of platinum (~2%) so that is a problem unless it could greatly reduced or less could be used, and finding another catalyst is important.

A piece of catalytic converter from a car might work but they still involve expensive rare metals.

In AGM batteries the gasses are to some extent recombined in the glass mat, and during overcharge the gas generation would be substantial. In NiMH batteries it recombines in some way through certain reactions in the electrolyte and metal hydride electrode [battery handbook 3rd edition]. I recall seeing some patents that apparently did not involve catalysts.

Over time if either oxygen or hydrogen is consumed in a way other than forming water there may end up being an excess of the other, which could accumulate to the point where venting to the atmosphere is needed, and the recombination mechanism could malfunction, so even a "sealed" battery needs a pressure activated release valve, and water loss can occur in that way as well. 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 Potential options that do not include platinum, and should be investigated more: A spark gap surrounded by anti-flash mesh. Causes combustion of the gasses but when the flame front propogates through a mass of stainless steel wool, heat is lost by conduction to the extent that combustion ceases. Therefore the combustion is confined to the small volume around the spark gap which is surrounded by the wool, but gas can still flow to and from the area. The electrical properties of the spark gap and the spark discharge could maybe be used to determine the pressure of gases in the battery, thereby allowing a microcontroller to estimate the spark frequency needed. Only one control module for a large battery bank would be needed so it could be manageable. One problem is perhaps the risk of detonation initiation. If detonation were initiated the shockwave would not be stopped by the wool, I think, and could cause the other gas in the cell to detonate. This may be manageable with informed design. In welding there are arrestors attached to the acetylene tanks which can arrest a shockwave so they should be investigated and maybe that mechanism used .

Another option might be to have a very small volume of gas space in the battery so even if it did detonate there is no harm done. Spak gap erosion has to be taken into account but it may be too slow to be a concern.

Maybe turn electrodes so they are horizontal instead of veritical so taht o2 bubbles up to the other electrode so it is present when h formed and helps recombination

General info on recombination and catalysts and how to make use of them practically:

http://www.freepatentsonline.com/5290640.html
http://www.freepatentsonline.com/5506067.html 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?
http://www.freepatentsonline.com/4383011.html 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.
http://www.freepatentsonline.com/4908282.html
http://www.freepatentsonline.com/4098964.html catalyst info
http://www.freepatentsonline.com/4374907.html preventing water on the catalyst surface
http://www.freepatentsonline.com/3622398.html 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
http://www.freepatentsonline.com/6254841.html
http://www.freepatentsonline.com/6333123.html
http://www.freepatentsonline.com/7722834.html catalyst

Sealed battery doc describes way to make catalyst but takes a lot of platinum

http://www.freepatentsonline.com/3630778.html Osmium and iridium might be cheaper
http://www.freepatentsonline.com/6500576.html
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

Battery Basics [1]

Nickel-Iron Battery/Research Development: Difference between revisions

Revision as of 19:39, 18 July 2011

Contents

Products and Projects

Commercial Ni-Fe Suppliers

Edison's Batteries

Anode

Cathode

Electrolyte

Cell Casing

Ed's Workshop

Anode

Cathode

Electrolyte

Cell Casing

Other

noonco

Source Materials

Nickel Compounds

Iron Compounds

Electrolytes

Notes

May 19

SECONDARY BATTERIES - NICKEL SYSTEMS Electrodes: Nickel

may 21

Sealing the battery

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