Turquoise Energy Ltd. News #24
Victoria BC
Copyright 2010 Craig Carmichael  -  February 1st 2010
http://www.TurquoiseEnergy.com

Highlights/Contents:

   January in Brief (summary)

   Electric Hubcaptm Car Drive System Project Detailed Report
      *

   Mechanical Torque Converter Project Detailed Report
      *

   Microcrystalline Ceramic Motor Coil Cores Project Detailed Report
      *

   Turquoise Battery Project Detailed Report
      * February Battery Experiments
 
    The Lead-Acid/Sodium Sulfate Battery Renewal Project January report
      *

Newsletters Index/Highlights:     http://www.TurquoiseEnergy.com/TENewslettersIndex.html


Construction Manuals for making your own:

* Electric Hubcap Motor
* Turquoise Motor Controller (latest rev. 2009/12/30)

are at http://www.TurquoiseEnergy.com/

January in Brief

   Reflecting

The Electric HubcapTM Vehicle Drive System
February Details


   I did do a little shopping to source out an axle and bearings idea.

Axles, Hubs, Bearings

   I went into a store and looked at some packages of trailer wheel bearings. Just to play with ideas, I bought a package of 1" bearings with two bearings and the outer races for them (along with a cotter pin,

Mechanical Torque Converter Project:
Torque Leverage Without Gears
February Details
Turquoise Battery Project
January Details

February Experiments

   In the last week of January I had put together a "ClO4-Mn" battery and started charging it at low current as the first stage of the "burn-in". Following this, like most of my batteries, it didn't seem to hold a charge. It seemed I'd put in the right sorts of chemical, in reasonable proportions. The lead acid batteries had all the right chemicals, but they needed deep cycling to "renew" them. Seems there are forms of chemical 'trickery', and there are proceedures for burning in some types of batteries. Perhaps there were similar things I had to do to my own batteries to get them to work?

   First I upped the current to around 30mA. Soon the cell had over 5 volts across it. Seemed ridiculous. Then I shorted the cell for a while. Then I charged again and it didn't semm to do much differently. Then I reversed the polarity. I expected the voltage to start at some value and work its way up. Instead it quickly reached (-) 3-1/2 volts and worked its way down, at first quickly and then gradually (seconds, minutes) to 1.9 volts. That's about the voltage it should have risen to and stopped at when connected the other way around!


Using

I look


"Burning in"

    Wrappi

Lead-Acid/Sodium Sulfate Battery Renewal Project
January Details

Glued-on Lids:
How and Why the Battery Makers Are Likely to Try to Prevent People From Renewing Batteries

   When I first started talking about the fact that lead-acid batteries can last far longer simply by adding a sulfate salt, sodium sulfate (or alum - known at least before WW II), to the acid, there was some incredulity on at least one battery related list group that such a thing was possible, because if it was, battery companies would have started using it long ago.
   However, if lead-acid batteries were to last 5 times longer, the sales would drop by almost 80%. The economics of this is obvious: one company might gain a very temporary competitive advantage by bringing them out, but soon sales of all lead-acid batteries would go way down, even while usage of them would rise as it became apparent they are more practical than they were. In fact, one person recently commented "These days it's as if they have a timer in them. Five years and "boom", that's it!"
   And all this is true even ignoring the probability that the battery companies are tightly under the thumb of "big oil" (via proxy share ownership with no obvious connection), who definitely don't want to see ordinary lead-acid batteries become a viable alternative to gasoline.

   Now to my surprise I have come across a battery with the lid glued shut. Once people have discovered the sulfate salt advantage, the battery companies may very well start gluing the lids on all lead-acid batteries so nothing useful can be added to them. They will claim it's for safety reasons.

Battery Renewal - my "Missing Links" Found

   I was sure sodium sulfate had to be a better sulfate salt additive for lead-acid batteries than alum or epsom salt, but I had been puzzled why I wasn't getting better results.
   The short story is:
   First, it seems that while it's great to just dump the salt in a relatively new battery to prevent deterioration, for deteriorated old, corroded ones, one must dump them out and clean out the crap. A lot of lead oxide, along with corroded-off pieces of plates, accumulates and messes things up. (Dump it into a plastic storage container or plastic pan, then funnel the acid into a bottle. Let it sit and clarify.)
   Second, it appears the batteries need to be "deep cycled", run down with a load to 8 or 9 volts and then charged up again. When I was only running them down to 11 volts, the improvements were slow coming and minimal.
   Furthermore, it appears the charger I have has been overcharging the batteries, doing them more harm than good in the process. I have only just now caught on to this.

   I also ran a battery right down to nothing, almost 0 volts - an "ultimate" test. (0.061V) It appeared that that had killed one cell, but the others operated at full capacity, with the battery supplying a load for the full time but two volts low. From this I conclude that running the batteries down to any normal level where they're still doing work won't harm them. A person on an internet chat list with an electric car also says this. Ie, running the car on electricity until it has to be switched over to gas because it's actually slowing down on level pavement, seemingly will do no harm to batteries with sodium sulfate in the electrolyte. It takes away that "FRAGILE" label. That comfort gives much more leeway and range to electric driving powered with lead-acid batteries.

   Having finally come to these sorts of conclusions after several months, someone on an e-mail group, evidently speaking from long experience, has presented the following instructions, right along the same lines as my results have very gradually been leading towards. I wish he'd posted it earlier!

"Charge at 5 amps, let trickle down [sit] over night. Discharge down to 8 volts. Recharge/discharge 1X more. Charge third time and it should work well. Forget all the damn testing. You will go nuts."

He connected one car headlight for a discharge load - generally they draw 2 to 4 amps. He went on to say:

"Some guys I know have taken old batteries, (like laid in the woods for 10 yrs?) and rejuvenated by charging, with a volt meter for measurement. example: 1stX 9.6V max during charge. 2ndX 10.7V, 3rdX 11.6V, 4thX 12.9V, 5thX 13.4V, 6thX 14.2V, 7thX 14.7V. 14.4-14.7V shows it's taking a full charge."

   He also dumps out the acid and (presumably) cleans out the battery, then adds alum salt in water. (Don't forget I'm the first to see that sodium sulfate should work best, so you'll see most references so far are to alum, and a few to epsom salt.)

   His are the sorts of results I seem to be getting when all is going well. But my battery charger seems to want to fry them if they refuse to go above 14.5 volts - it just tries at full current to force them up, until they are merrily boiling away and the voltage is actually going down, down.

   The rest of this sub-heading is just the nitty-gritty of individual tests and results, then some how-to instructions are at the bottom.

   On December 5th I'd put a discarded battery having 15 grams of anhydrous sodium sulfate in each cell on my car. As usual, I hadn't reliably determined the capacity before adding the salt. It was seemingly about one amp-hour (AH), but it hadn't had a very good charging before the test. After the salt and some load tests it was working, but had only about 4 or 5 AH of storage capacity. In its best test of several, it had lasted just over 34 minutes supplying a 10 amp load, 5.8 AH. (I stop when the voltage drops to 11.00V. That's not 100% discharge, but the voltage generally starts dropping rapidly below 11-1/4 volts, so it must be the bulk of it.) The worst test went about 22 minutes, 3.6 AH. (Charging conditions and the amount of time they sit before the test varies.)
   I turned the idle in my car way down in 2006 to save gas, to just enough to keep the engine turning over. My driving is mostly in town (the great red light district), and as I was keeping track, it became evident that this measure cuts total fuel usage by at least 10% in city driving. It also means that the car doesn't charge the battery except when it's moving and in gear. Over time, the fuel savings exceeded the cost of a couple of used batteries I went through before hearing of alum. Batteries that won't wear out are thus of special interest, even just for the regular car battery!
   In the dark of winter with the headlights on much of the time, this battery, with its very limited capacity, after running a couple of good weeks or so, seemed to get progressively lower and lower over a week or so of mostly in-town night driving, the headlights getting dimmer when waiting at lights, and then it wouldn't start the car. With the low storage capacity, the periods of charging couldn't bring it up enough to last through the periods of discharging.
   I took it out and put in the previous battery (also beefed up with sodium sulfate). The 'discard' battery sat from around December 20th to January 4th, when I finally got around to charging it. Of course, leaving a lead-acid battery discharged is supposed to be the worst thing for it, and this battery had now been discarded twice as a "non starter". After charging overnight and then letting it sit all day of the 5th, I did a 10 amp load test in the evening. It ran over 38 minutes,  6.36 AH, breaking its previous maximum record and the 6 AH mark.
   I put the battery back on the 2 amp charge and left it on. 20 hours later it was still sitting there with 2 amps going in. That's 40 AH in, after putting out only 6 AH. With good batteries, whether or not they have Na2SO4 added, when it's fully charged the charging voltage goes up over 14 volts and the charging current drops to well under 1/2 an amp. Usually I would turn these batteries that keep on drawing current off after a few hours, thinking that was ridiculous inefficiency. [note: this was probably saving me from _some_ of the overcharging grief I seem to have been having.] But after 20 hours, the charger said 13.7 V instead of the 13.6 it had read the previous day. That seemed to be a change. I turned it off for a couple of hours, and then ran another load test. It went 55 minutes, 9.27 AH. That was 45% more energy than the previous day's record (and as much as a bank of 10 Ni-MH "D" cells!) - it was starting to seem like a real battery!
   So, either the charging or the cycling was definitely improving it. I put it on charge another 36 hours or so, then let it sit three hours, then ran another load test. The voltages were virtually identical, except the length of the test again stretched out: 62.5 minutes, 10.42 AH.

   But was it the continued charging, the cycling, or just time that was making the improvement?

Charging: The next test was to charge it for about 3-1/2 days, until January 12th, and load test again. The result was very close to the previous test, 10-1/2 AH - no improvement. Evidently long charging is just a waste of time and electricity.

Time alone: Batteries with sodium sulfate added that weren't being actively tested didn't seem to improve by themselves, so restoring them isn't just a matter of letting them sit until they're working well. It doesn't happen.

Cycling: Well then, how about cycling, and how about cycling to lower states of charge than I'd been doing by stopping at 11.00 volts? In the car the battery had gone to lower states of charge, and thereafter it had more amp-hours than before. Of course, it is supposed to be very bad for lead acid batteries to discharge them more than 60% or to leave them sitting below 12.4 volts for long time periods. I continued the discharge down to 8.00 volts, about another 1/2 hour. (Of course, the four headlights would be drawing somewhere under 10 amps at such low voltages.) When I ended this, the battery recovered to 11.83 volts in 5 minutes. It was thus less discharged than I'd expected.
   (Rough, typical no load figures once the voltage has stabilized: 12.7+ volts = 100% charged, 12.0 = 50%, 10.5 = (virtually) 0% charged.)
   The next time, the battery didn't last longer, but it ran 1/4 volt higher for most of the discharge cycle. Perhaps that was all this battery was designed for- it had no printed specs. But evidently, running the battery down does something good. So the next time I ran it down to 7 volts.
   On the next load test, again the time was about the same, an hour, but the voltage was better yet, staying well above 12 volts for most of the discharge. This seemed very healthy. Evidently the battery was fully restored, or fairly close to it.
   I decided to try the ultimate and discharge it to nothing. I left the lights turned overnight. The meter read .061 volts. It only gradually recovered to about 3 volts.
   I charged it up, but the voltage (with 2 amps charge current) wouldn't rise above 13.3 where it had been 13.6, and in the next load test it only went about 12 minutes until it dropped below 11 volts, instead of an hour. However, it ran along at over 10 volts for almost an hour - same length of time but down by around 2 volts from where it had been. It would seem one cell wasn't working right. The total discharge was definitely hard on it, but still it had some sort of life. That discharge would have been pretty much fatal to a non-treated battery, and I accidentally did it to one trying to do a "before" test. (That was when I first started and unfortunately I didn't keep that battery to try the "after".) Would this one recover? Only some more cycles would tell. I ran it down to 8 volts and put it back on charge for the night. Both times (from 0 volts and this time) I had to give it a few minutes of 15 amp charge to get it to come up to voltage before the charger (at 2 or 8 amps) gave up and cried "E01!" The charger is a very poor sport when confronted by the unexpected.
   Further tests revealed that the one cell continued to be a serious problem and couldn't be restored. But no one would intentionally run a battery right down to nothing - it would have long since ceased to move the car. Short of that, it seems the batteries can be discharged until the car won't perform without any reduction of battery capacity or damage. In my experience the total discharge condition will also wreck Ni-Cd cells, as the weakest cells are driven into reverse charge in the process, so perhaps it's no big surprise that it might also "do in" lead-acid cells, even treated ones.
   One thing I should have tried but didn't was to drain the battery and rinse it out. That might have cleared the problem.

   It seems the deep cycling works. Until I killed it by extreme, performance looked very good for a battery that was removed from a car twice because it wouldn't hold enough charge to start the engine. Somehow, "sulfated" areas of passivated electrode plate are restored to electrochemically active operation with the cycling, and the battery gets restored to what is evidently full life again.
Sodium Sulfate Chemie: The Likely Cleaning Reaction

   Although AL+++ in alum and Mg++ ions in epsom salt do stay in the solution in acid (unlike alumina in water or alkali), the +1 valence of Na+ ions seems a better candidate to exchange with H+ ions in acid solution reactions.

   In the electrolyte, we add just a bit of sodium sulfate salt, Na2SO4, yielding Na+, Na+ and SO4--. It seems almost inevitable that this would convert to mainly acid with just a bit of NaHSO4 - sodium bisulfate. The fact that the bisulfate is acidic, pH 1, and that (as I discovered in September) the battery pH rapidly returns to "1" however much salt is added, supports this assumption.
   The effect of sodium bisulfate is probably similar to that of sodium bicarbonate (NaHCO3, baking soda), (whatever effect that is), and a key ingredient in the renewal process. However, the bicarbonate has a mildly alkaline pH, while the highly acidic bisulfate is compatible with the H2SO4 electolyte. Baking soda in water is sometimes dumped in to clean lead battery plates after draining the acid. Here we have a "baking soda" that can be left in the battery all the time to clean it and keep it clean, continually, effortlessly - Wow! ("Stewing soda"?)
   What a great electrolyte additive!

   By contrast, MgSO4 won't form any "bi-" anything, and alum would have to dissolve into 1/4 as much sodium bisulfate and AlH(SO4)2, which, without trying to figure it out, looks to me a lot less able to react and hence less useful.
Latest Lead-Acid Battery Renewal/Innoculation Instructions

1. Please see Turquoise Energy News #22 for battery safety and salt filling instructions. ALWAYS WEAR GLOVES AND A FACE SHIELD OR GOGGLES - THE ACID WILL BLIND YOU as well as badly burn your skin. Don't wear clothes you care about. Work outside near a garden hose if possible.

2. If the battery is pretty new, skip steps 2 and 3: just add the salt. If it's old and not working well or at all, Shake the battery to stir up the sludge off the bottom and drain the acid into a plastic pan or plastic storage container, then funnel it into a bottle. Pour in water and shake out more sludge into the pan until the water comes out fairly clear. You can leave the water until the lead sludge has settled and it's clear, then pour the clear water off.

3. Leave the acid until the sludge has settled to the bottom of the bottle and the liquid is clear. (takes hours) Then funnel it back into the battery cells without the crap at the bottom. Top up the battery with a little sulfuric acid (most any battery place has it) or pure water.

   My best suggestion of what to do with the sludge - lead oxide powder, bits of plate et al - is to dump it into some old battery you don't want and then take that in for recycling. That way, it gets dealt with in whatever way is usual at the battery recycling place - presumably it's reused in new batteries. When you're down to trace amounts dirtying your containers... at some point it's just "dandruff" that's not worth worrying about. Wash them out.
   Of course, the best thing to do is to put sodium sulfate in new batteries so they don't get like that in the first place.

4. Again, for quantity, I'm estimating a good ballpark figure for 12 volt batteries seems to be: 1 gram of anhydrous sodium sulfate [drug store, compounding pharmacy] per cell, for each 2 pounds of overall battery weight. Thus for a 30 pound car battery, 15 grams or a bit more per cell, 90 grams total. Double per cell for a 6 volt battery. For a size "27" 12 volt battery, about 50 pounds, perhaps 25 to 30 grams per cell.
   That's just a guesstimate, no guarantees. There's probably a fairly tolerant acceptable range, and the best range may vary a bit from battery to battery.

5. Another previously missing link in my instructions: Charge the battery, leave it sit a few hours, then run it way down to 8 or 9 volts. (Use a volt meter.) Do it again, and the voltages or running time should be increased. After a couple of times (several times if it's in bad shape), it should be up to most of its full capacity. Don't overcharge (My charger was frying them), and don't let the battery voltage run down to nothing - a cell(s) may go bad.

http://www.turquoiseenergy.com
Victoria BC