Battery chemistry comparison
The other battery chemistries deserve a fair shake as well. There may be even more (developed) battery chemistries than this and I may add more in the future.
In summary, it looks like zinc bromide might be a very attractive option, quite possibly superior to nickel iron for OSE purposes. But more research is needed to ensure there are no snags. Also a question mark remains as to why it is not already used as a secondary battery in e.g. backup power systems etc. very much.
Lithium titanate and lithium iron phosphate might also be an option if it is not still patented, but lithium has supply issues that conflict with OSE goals so I did not look further into pricing of the materials. These 3 and nickel iron currently appear to be the most practical options and it seems unlikely that further research will change that.
Sorry everything is a complete mess, I may clean it up later if I have time.
Went to wikipedia and go the list below:
* Flow battery very interesting o Vanadium redox battery maybe o Zinc-bromine flow battery bromine rare? Needs double checking, also if diff ions in half cells electrolyte contamination may limit cycle life * Fuel cell no too expensive, * Lead-acid battery excluded, trying to find something better * Lithium air battery no in dev * Lithium-ion battery no cobalt excluded for cycle life and cost rarity o Lithium ion polymer battery maybe see notes * Lithium iron phosphate battery maybe see notes * Lithium-sulfur battery no in dev * Lithium-titanate battery maybe * Molten salt battery maybe probably not * Nickel-cadmium battery no enviro reasons and cost o Nickel-cadmium battery vented cell type * Nickel hydrogen battery maybe see below * Nickel-iron battery of course * Nickel metal hydride battery no, no better than nife for out purposes, short cycle life, though note that ingredients are not that rare, the rare earth metas fairly common but not as good as iron of course o Low self-discharge NiMH battery * Nickel-zinc battery need to check still, cycle life low due to shape changes of zinc but why not do the same as for the zinc bromide battery and completely discharge periodically? * Organic radical no battery in dev * Polymer-based no battery in dev * Polysulfide bromide battery bromine rare? no in seawater and $4.5 per ton see wik article, * Potassium-ion battery maybe * Rechargeable alkaline battery no cycle life low * Sodium-ion battery no n dev * Sodium-sulfur battery maybe high temp has issues * Super iron battery no cycle life low * Zinc matrix battery no in dev
Even the following list is incomplete.
Salt water batteries are gaining popularity (2016) for their chemical simplicity, stability, ease of manufacture, and recycling. Volumetric efficiency does not compare well to other chemistries for high discharge needs, but a small battery closet is sufficient for most cases and they have lower DoD (Depth of Dishcarge) than most other batteries while still maintaining a good cycle life. One of the more popular chemistries is listed below, but other chemistries using aluminum etc. have been experimented with.
Anode: activated carbon composites Cathode: Manganese Oxide spinel Separator layers: unwoven cellulose (cotton) Eloctrolyte: aqueous Sodium Sulfate
Perhaps it well be easy to 3D print cases, easily CNC machine parts, and mine the common minerals for such batteries in the near future.
lithium ion titanate patents to see if lithium titanate still under patent and find ou tmore about manufacture:
searched" abst/"titanate" lithium battery" ordered chronologically and some others which were more specific, but it it regards lithium titanate batteries it should probably match that string yesh, abst/ indicated term must be in the abstract
http://www.freepatentsonline.com/5545468.html seems to be the earliest one 1996 so the patents on the basic technology mentioned in it might be expired by now, regardless of whether it is th original patent presumably the technology mentioned has already been patented by this date http://www.freepatentsonline.com/7879493.html http://www.freepatentsonline.com/7931987.html http://www.patentstorm.us/patents/7368097/description.html
http://en.wikipedia.org/wiki/Lithium_ion esp the titanate ones although depends on if the other ones like iron phosphate or spinel ones could be rejuvenated practically, get prices for everything for the different types, also vheck patents for som mfr procedures to determine complexity, check prices on protection circuits texas instruments, also the shutdown separator(safety section) if is anything special http://en.wikipedia.org/wiki/Potassium_graphite material needed for one electrode
mfgr complexity: lookup some patentents, also note the materials used in mfgr processes so can find prices on alibaba
Cost of materials per kWh for titanate:
PhosphateL issues: electrolyte degradation, manufacturing of the electrode materials "lithium iron phosphate (commonly used in fertilizers)" from wik aryicle In the patent lawsuits in the US in 2005 and 2006, UT and Hydro-Québec claimed that every battery using LiFePO4 as the cathode and the cathode material used in some lithium ion batteries infringed their patents, US patent No 5910382 and 6514640. The ‘382 and ‘640 patents claimed a special crystal structure and a chemical formula of the battery cathode material. On Dec 9th, 2008, European Patent Office revokes Dr. Goodenough’s LiMPO4 patent, patent number 0904607. Similar to lithium oxides, LiMPO4 may be synthesized by the following methods: 1. solid-phase synthesis, 2. emulsion drying, 3. sol-gel process 4. solution coprecipitation, 5. vapor phase deposition, 6. electrochemical synthesis, 7. electron beam irradiation, 8. microwave process 9. hydrothermal synthesis, 10. ultrasonic pyrolysis, 11. spray pyrolysis, etc. Different processes have different results. For example, in the emulsion drying process, the emulsifier is first mixed with kerosene. Next, the solutions of lithium salts and iron salts are added to this mixture. This process produces carbon particles of nano sizes . Hydrothermal synthesis produces LiMPO4 with good crystallinity. Conductive carbon is obtained by adding polyethylene glycol to the solution followed by thermal processing . Vapor phase deposition produces a thin film LiMPO4 . patents might be a deal breaker , depends, high performance battery tech would be patented, but maybe not the llower performing low discharge rate that we want search patents for the cehmical formula or olivine and find out when they expire "^ "LiFePO4: A Novel Cathode Material for Rechargeable Batteries", A.K. Padhi, K.S. Nanjundaswamy, J.B. Goodenough, Electrochimical Society Meeting Abstracts, 96-1, May, 1996, pp 73" if iron phosphate itsself was novel in 1996 it would have been patented pretty fast, how long does the patent last? can also do the same for other discovery milestones, find the sci docs or when it was first discovered and assume they got the longest lasting patent they could on it at that time, do the same for titanate http://www.thermograde.com/our-products/lithium-titanate/prod_16.html Li 2 TiO3 Formula Name: Lithium Metatitanate
"^ "Phospho-olivines as positive-electrode materials for rechargeable lithium batteries". Electrochem. Society 144: 1188–1194. 1997. http://scitation.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=JESOAN000144000004001188000001&idtype=cvips&gifs=yes.
costs: wikipedia article on iron pphosphate says that with addition of carbon 95% of theoretical utilization of active material can be realized, so assume 80% or so maybe http://webcache.googleusercontent.com/search?q=cache:qAxMZsm9OOkJ:www.meridian-int-res.com/Projects/How_Much_Lithium_Per_Battery.pdf+http://www.meridian-int-res.com/Projects/How_Much_Lithium_Per_Battery.pdf&hl=en&gl=ca ayAY SAYS 2 to 3 kg of lithium carbonate technical grade for 1 kWh Current global LCE production of circa. 100,000 tonnes, if available, would therefore be sufficient for 2 to 3 million PHEV batteries of 1 6 kWh capacity (GM Volt class). Doc indicates it may be lower for lower drain rate batts , the doc has serious mistakes in it like"If we look at the theoretical specific energy of a LiIon battery, the figures widely quoted are between 400 and 450 Wh/kg. The actual specific energy achieved is between 70 and 120 Wh/kg. Therefore practical LiIon batteries are using some four times as much Lithium per kWh as the “theoretical” quantity or more." which is idiotic, much of the weight is due to other components especially the other electrode nwtc.
"Therefore the generally quoted figures for the capacity of the LiFePO4 material of 170 mAh/g are at low discharge rates of 0.1 C or less – this is a theoretical figure. Looking at the C/3 discharge rate which might occur in a large pure EV battery, capacity falls to 130 mAh/g. Let us take a 10 kWh PHEV battery and assume a maximum speed in EV mode of 60 mph and further assume optimistically that at that speed range of 3 miles per kWh is obtained i.e. 30 miles nominal range for complete discharge – that is discharge in 30 minutes or a 2C rate. It can be seen that capacity declines to 90-100 mAh/g or d"
when they say "graphite" it miht require that the cell be manufactured with lithium graphite like calcu mgraphite check patents on lithium batts specifically coud be the cobalt ones even "Irreversible capacity loss also occurs in the cathode. LiIon batteries are manufactured in the discharged state with no Lithium in the carbon anode and the LiMO2 oxide or LiFePO4 cathode fully lithiated." mayeb can do the same with potassium ion? , they keep confusing enegy with charge, this document isnot reliable, need to get actual figures regarding actual manufactured batteries also for the supply of lithium etc. " Therefore again the “theoretical” energy density of a LiC6 anode with one Li atom present per six Carbon atoms cannot be achieved in the real world. The “theoretical” charge density of LiC6 is 372 mAh/g if all of the Lithium atoms in a sample could be discharged and do work. Sony's consumer battery carbon anodes provided 180 mAh/g nominal capacity at low discharge rates or less than 50% of that theoretical storage capacity"
|Another factor that must be allowed for is the processing yield to purify raw technical grade Lithium Carbonate into purified low sodium (99.95%) Lithium Carbonate required for the manufacture of batteries. The technical grade Li2CO3 produced from Atacama contains about 0.04% Sodium (Na). This has to be reduced to below 0.0002% Na for use in batteries. In some cases ultra high purity 99.995% Lithium Carbonate is required.] While yields of over 80% are possible on a laboratory scale, this is more difficult to achieve industrially particularly as purity control requirements increase. 70% may be a more realistic yield figure to use" Compare with closes commercial option, i.e. something made for stationary large capacity low discharge rate use
http://sciencelinks.jp/j-east/article/200704/000020070407A0043690.php would tell more about the graphite needs http://www.meridian-int-res.com/Projects/Lithium_Microscope.pdf "the trouble with lithium" substantial supply issues, not localizable resource though not they might bot bebetter than nickel so need to chek "Substituting other metals for the iron or lithium in LiMPO4 can also raise its efficiency. A123 and Valence reported the substitution of magnesium, titanium, manganese, zirconium and zinc." other metals fo lithium? like K and Na as an example I guess.
cost of materials :
mfgr complexity: lookup some patentents, also note the materials used in mfgr processes so can find prices on alibaba
Compare with closest commercial option, i.e. something made for stationary large capacity low discharge rate use Media player batteries, useless indicator
http://en.wikipedia.org/wiki/Lithium_iron_phosphate_battery also indicates to 7000 cycles ned to check calendar life No lithium remains in the cathode of a fully charged LiFePO4 cell—in a LiCoO2 cell, approximately 50% remains in the cathode. LiFePO4 is highly resilient during oxygen loss, which typically results in an exothermic reaction in other lithium cells. check that reference fo info on thermal runaway since that is the main safety problem ^ A123Systems "...Current test projecting excellent calendar life: 17% impedance growth and 23% capacity loss in 15 [fifteen!] years at 100% SOC, 60 deg. C..."
note lithium iron phosphate are already at 2.5 wh per $ show ebay link they are new batts, made for solar?
check the max size of cells thing
cobalt http://www.lme.com/minormetals/Cobalt_Prices.asp cobalt maybe 3 times the price of nickel
http://healthlibrary.brighamandwomens.org/RelatedItems/19,Cobalt?PrinterFriendly=true Polycythemia, an increase in red blood cells, may be a symptom of cobalt excess. Untreated polycythemia can result in congestive heart failure. search pubmed for cobalt toxicity for better quality info including reports on excess intake of suplements, searched on ppubmed a bunch of terms like "tocicity cobalt"| cobalt toxicicty including just in the title/abstract and nothing at all
inadequate supply and increasing demand for lithium fro batteries might actually be a substantial problem though is not clear aand nickel is not more common in the earth's crust, it might be easier to obtain or something, chekc for sodium ion or something, in other words price might go up or it mightbecome more expensive in the future as the supply runs out though the market price should be incorporating tha tinformation right now check prices of lithiu batteries for stationary use
might asa well start by computing the cost benefit of hihger efficiency with other chemistries sinc if it is low not much point in doing all tha tresearch
vanadium redox price of vanadium s http://www.australianminesatlas.gov.au/aimr/commodity/vanadium_09.jsp 3 to 4 bucks a pound toxicity might be poorly known whic is a risk itsself also solution not paste so more hazardous , need the proton exchagne membrane too shoudl be relatively cheap though ion exchange membrane is cheap http://www.energystoragenews.com/Vanadium%20Redox%20Flow%20Batteries.htm says efficiency is more like 65 percent so no better than nife (the company probably means DC surely they will make the claims as favorable lookin as possible though maybe not "Vanadium is a comparatively abundant element with crustal atomic abundance of 75,000 ppb (compared to 22,000 ppb for copper)." http://www.freepatentsonline.com/4786567.html http://vanadiumbattery.com/index.php/technology/index/ " Commercially available V2O5 is only slightly soluble in sulfuric acid" # Individual cells in a stack may have different numbers of built-in elements; this is important when a sinusoidal output is created using the switching method " they may be switching between different cell configurations rapidly to do the inverting could make sense, since the batteris have a very fast response time compared with other chemistries
http://www.patents.com/us-5318865.html van redox
Info needed on vanadium toxicity, also remmeber because it is dissolved much worse, also low solubility migh mean impractically large tanks
zonc air http://en.wikipedia.org/wiki/Zinc-air_battery no, rechargeable still in development
nimh, not because the positive electrode requires rare metals, double check whic metals and their prices , also efficiency is no bettery than nife and doesn't last as long and harder to make possibly, nickle hydroxide needs to be in the right crystal form , also needs cobalt additive
al air, primary doesn't last
other redox flow batteries esp iron iron iron (+3)/ iron(+2) (U.S. Pat. No. 4,069,371; U.S. Pat. No. 4,053,684) not the advantage of having both half cells the same element, mixing problem between sides is obviated , remember we are sticking to existing technology though , if microporous could use teflon or polyethylene ultrafiltration films hollow fiber maybe similar cheap films, patents indicating that it has practical problmes also is hard to find info on it and it is not listed in any of the artciles that mention th ecommon flow batteries, was probably abandoned due to practical difficulties and not developed.
iResults of this cycle testing can be briefly summarized as follows: (1) coulombic efficiencies are in the range of 85% minimally to over 95% under controlled conditions; (2) polarization voltage losses are in the order of 7%, or less than 10% of the total charging potential; (3) An example of a charge and discharge curve for the series of VP-HDPE membranes of Table II is shown in FIG. 5, in which a coulombic efficiency, defined as ampere-hour input over amper-hour output, of 91% was obtained. Probably doesn't have to be gama from cobalt 60, xrays might be useable instead , or electron beams maybe also note that for microporous that might still be useful thes might actually be easier ti make than nife , says carbon electrodes made at GEL using"wil-mat_ method http://www.freepatentsonline.com/4468441.html separator and info http://www.freepatentsonline.com/4414090.html separator and info http://www.freepatentsonline.com/4069371.html reffed to in first http://www.freepatentsonline.com/5439757.html reffed to also check the related patents list, info about other redox flow batteries and their limitations cost of materials :
Nafion cation-exchange membrane. check price
mfgr complexity: lookup some patentents, also note the materials used in mfgr processes so can find prices on alibaba
Compare with closest commercial option, i.e. something made for stationary large capacity low discharge rate use
ni-h, platinum needed?, very long life 85% eff , knit zirconia cloth? does it have to be or would glass do needs more research , article on the gas http://en.wikipedia.org/wiki/Gas_diffusion_electrode indicates silver or carbon even might work, teflon needed? read about often in patents etc maybe common checked battery handbook and not a word about other catalysts maybe not possible, 6 "The platinum content is normally specified as 7.0 � 1.0 mg/cm2." that's a lot, woudl def needa differend catalyst material http://www.aero.org/publications/thaller/thaller-1.html The NASA Handbook for Nickel-hydrogen Batteries provides an excellent historical review of this technology, and readers are referred to that document for a more in-depth treatment of this topic.1.1 other catalysts: "Raney nickel"? might try looking at patents on nickel hydrogen there are lots
nickelmetal nydrode battery with the hydrogen electrode exposed to hydrogen reservoir periodically or by diffusion in the water, metal hydride has to be mh not mh2 so need to split h2 molecule maybe what catalyst does maybe the h2 would have to be under extremely high pressure or something
http://en.wikipedia.org/wiki/Flow_Battery several interesting ones iron titanium common materials , iron-iron is also used see patents elsewher in these notes
patents : http://www.freepatentsonline.com/5807643.html k ion very interesting might still be covered by patents though also potassium graphite pyrophoric more investigation needed http://en.wikipedia.org/wiki/Potassium-ion_battery interesting indeed, millions of cycles supposedly wonder if info is available on it though , they are in commercial manufacture for for media players, further research needed for flow cells maybe could have only a few cells and then step up the voltage but would introduce inefficiencies to avoid electrical shorting between cells, laminar flow tank, eelctrolyete probably warmer when comes out of the cell , maybe mechanisms to transfer electrolyte that do not allow current leakage like scooping etc. maybe augers
http://www.sciencedirect.com/science/article/pii/S0378775303008954 says only 500 cycles , seems t obe the first time the battery was described but can tbe sure, in 2003 "Potassium secondary cell based on Prussian blue cathode " the 2 patents in the wik article are broken links apparently and searching the patent numbers on freepatentsonlin turns up nothign and they are too long for patent numbers I think
just preas to not be much inf oavailable on these and are probably still under patent molten salt, high temperature probably not practical large insulating layer higt temps cause all kinds of problems needed check cost of it with fibeglass from home depot, very high self discharge rate even with r 50 insulatino usually resevre but migh tbe some secondary ones
thin film rechargeable lithium, looks interesting, long cycle life but looks hard to make large amounts, coudl be wrong about that though deposition of e.g. aluminum on mylar os cheap, but maybe not by weight of the reactant roll-to roll supposedly reduces costs as compares with normal lithium ion so maybe thety would nto be sor ard to make
lipoly might be inherently safer, easier to make , no low cycle life at 500
also check price of flouride containing material maybe for flouropolymers and the k-ion electrolyte stuff which was KBrF material maybe it could be something else though it is mentioned that electroytes used in lithium ion would work fine too. But the breakdown of the electrolyte is one of the mechanisms by which litium ions wear out so could be a problem if others are used.
ZnBr type of flow battery the zinc plates out so little advantage as a flow battery, still limited by electrode size, eff only 75% , electrolyte the same both sides so contamination not a problem, says can provide at lower cost than van redox and others , check handbook of batteries for info might be cheaper on a kwh basis though needs to be verified
bromine doesn't sound too bad toxicity wise like chlorine, lithium bromide was a problem though remember with air conditioning systems.
remember coloumbic is charge only, polarization and other things can lower voltage so will lower the overall efficiency below the coloumbic eff
Elsewher in patents the coloumbic efficiency is defined as charge out/charge in so excludes voltage, energy eff is bound to be less thatn coloumbic ,
http://www.chemeurope.com/en/encyclopedia/Flow_battery.html s in the fact that all cells share the same electrolyte/s. Therefore, the electrolyte/s may be charged using a given number of cells and discharged with a different number. Because the voltage of the battery is proportional to the number of cells used the battery can therefore act as a very powerful dc-dc converter. In addition, if the number of cells is continuously changed (on the input and/ or output side) power conversion can also be ac-dc, ac-ac or dc-ac, with the frequency limited by that of the switching gear. general on flow
from battery hand book : For utility applications battery efficiency is a primary concern, and percent utilization is about 50 to 70% to maximize efficiency. For electric-vehicle applications battery size and weight are more important, and the percent utilization can be as high as 80 to 90%. so efficiency must be less than that "on total energy requirements of auxiliary systems, although the energy devoted to auxiliaries is projected to be less than a few percent of the total battery energy. ther is a graph with energy efficiency and it doesn look like roughly 74% overall is right need to verify cycle durability complexing agents just amnium compounds Makin ghte electrodes:
GEL using"wil-mat_ method?
http://www.freepatentsonline.com/6509119.html http://www.freepatentsonline.com/5626986.html looks good more patents: large number of them , just search "zinc bromide battery" "zinc bromine battery" "zinc bromine flow battery" "abst/zinc abst/bromine abst/battery"etc. http://www.freepatentsonline.com/3811945.html issues: http://www.freepatentsonline.com/4343868.html change of ph (1982) http://www.freepatentsonline.com/4206269.html http://www.freepatentsonline.com/3811945.html shape change o http://www.freepatentsonline.com/3972727.html shape chages of zinc , can also be avoided with deep discharge and refomation of the electrode, could have more than 1 battery and cause one to deep discharge while the other is still charged at a useable level. Could be doen wit hcells in a battery, on battery beign given the treatment with the help of a dc-dc buck converter or something
Doesn't look like the microporous or ion exchange membrane shoudl be too hard to make, many ways to make them, grafted polyehtylene maybe? maybe not that was for iron-iron, the ion exchagne membrane nafion is IIRC the same stuff as ion exchagne beads and shoudl be makeable
looks good and reasonably simple, with a better membrane(ionic probably available) would be more efficient, could also use separate electrolyte storage tanks for the cells woudl simplify design too. could b easier to make since there is no pasting in or nickel plating, all plastic components inthe battery except the electrodes. Essentially eliminate the pumps etc. and just make it abattery, depend on convection maybe for electrolyte flow as the 15% of energy not converted to electricity woudl be converted mostly to heat apparently (little gassing, althoguh gassing would coause convection too). CoMaybe they could be made of activated carbon or graphit powder or flake rammed into a perforated plastic tubes under sufficient force,also there mgith need to be some chemical treatment of the surface to introduce appropriate functional groups as some sort of catalyst apparently. Also maybe the electrodes and separator could be reused for other battery chemistry types like iron-iron down the lines?
Extremely available and low cost components. Looks like an old technology ou of patent http://www.freepatentsonline.com/3811945.html (1974)
polysulfide bromide battery balso a flow battery , contamination from dif electrolytes probabl yleads to short cycle life though need to look up more info about it, http://www.diracdelta.co.uk/science/source/c/o/coulombic%20efficiency/source.html says efficiency is low http://www.freepatentsonline.com/6511767.html patent on the electrodes http://www.ihatebatteries.com/BatteryHistory/ says was experimental and not finished U.S. Pat. No. 4,485,154 polysulfide bromine