Comments on the ALABC 2016-18 Overview project

[PNjunction]

For years I've been watching the ALABC with interest in regards to improving primarily VRLA AGM's.

At first, it was identifiying and trying to resolve the PCL 1 / 2 / 3 modes. This was with PLT, or pure-lead-tin vrla's and now kind of a return to lead-carbon, ie the Ultrabattery, primarily done to resolve vehicular issues in high-rate-partial-state-of-charge, or HRPSoC, which the ultrabattery is tackling the latest PCL3 mode. (insufficient charging of the negative plate, due in part to the VRLA design itself to actually function with recombination).

I am brand agnostic, but let me say that I'm familiar with Optima, Odyssey, Enersys, Hawker, Cyclon "tppl" pure-lead batteries in general. It was their performance that actually led me to LiFeP04 studies. I'm very happy on either side of the chemical fence, as long as one knows the pros and cons. East-Penn agm's are no stranger to me either, along with a string of others. Brand here is not really important for the discussion.

For those interested, the overview presentation can be found here:

http://www.alabc.org/

Advancements in Pb are one thing, but to survive and thrive amongst lithium based batteries are another. This is the main question as how to increase Pb performance, keep the price reasonable (anyone can make a million-dollar NASA battery), and be able to integrate it easily into real-world products. I'll let you read it.

Here is the comment from the peanut-gallery, um me:

Currently lead-acid is DUMB - but what do I mean by that? Well, most Lithium products are smart with attending charge control built in! (well, the exception of my own LFP system using ME as the brains of the outfit, aside from an external LVD etc, but I digress....)

Unlike most lithium based products, Pb is considered as a power source that sits at the end of the line (or beginning if you prefer), subject to the whims of it's owner or charger. There is no immediate feedback to the chargers. Ie, not smart. AFAIK, BMW has a smart system in place where the charger is calibrated to a known battery, BUT is it getting feedback *directly* from within the battery itself?

To cut to the chase, if Pb is going to survive into the future, R&D is great trying to make it better, but for the average joe, who couldn't give a rat's *ss about charging, put some smarts into the battery itself - AND have it cooperate with the charging system.

My commercial 2-way radios that live on NiMh and Lithium (4.2v nominal chemistry, not LFP) are doing GREAT in a smart Motorola Impres charger. There is a uP in the battery that keeps track of things, and directs the charger to act differently depending on the environment I'm putting those radio through.

So what I'm envisioning is the addition of a smart uP or other device in the battery itself which can do - I dunno' - keep track of date from manufacture, coulomb counting, you name it to participate with the vehicle's own charging system.

On a smaller scale, since they also mention energy storage, how about cooperating with a very smart solar charge controller?

Thing is, I'm doing fine manually overcharging my positive plate and getting the negative fully charged once a month or so with my own desktop bench charger (usually allowing for a 14.4v "absorb" or more properly the CV stage continue well beyond zero current for many hours.) The small amount of positive corrosion offsets the sulfation of the negative plate.

But who does this other than geeks? Take this error-prone process out of my hands, please!

If you make the CURRENT line of Pb products smarter, by engineering some built-in monitoring / status circuitry to cooperate with a matching smart charger, you may not have to reformulate at all for us peons.

[PNjunction]

ALABC and Charging Waveforms With Solar Charge Controllers

Like circling the event-horizon of a black-hole, I am hesitant to go here, but I'll ask since no reputable electrochemist will touch this in public.

Since the ALABC is concerned with both vehicular AND renewable energy, as a solar user I am forced to ask:

Since 99.9% of the solar users in the world rely on PWM, (either directly with inexpensive controllers once they reach CV, or with MPPT who also use PWM during the CV phase), what effect does this waveform have on Pb batteries, in regards to the passivation layer? Something that lithium has too, albeit different form, but the end result is the unwanted secondary reaction of the chemical process. (Prof Jeffery Dahn's win series on lithium was instrumental to me, but back to Pb..)

Lurkers probably know where this is going, but stay tuned...

Has anyone read the "FULL" independent 1998/1999 test report from Professor Tadeusz Malinski, P.H.D. from Ohio U? (formerly at Oakland U) in regards to so-called pulse-charging? What I'm talking about here is NOT a high-voltage/high current charge pulse, but one that seems to have *some* effect on the passivation layer.

I'm sure you have. It is part of the *original* so-called desulphators which every copy-cat hanger-on and diy'er looked at the pretty pictures and thought they too would like to be tickling a battery without understanding a thing about the text. Unfortunately, they take it out of context, and try to revive trash which should remain in a buried (recycled) state.

Far too few use it properly, to keep a good battery healthy. Since I can't get my hand on an UltraBattery, I resort to an off the shelf product with reputable testing behind it - although one has to look for the FULL report, since abbreviated versions, and second-hand accounts sound like just another marketing strategy. Prof. Malinski is easy to find. Many accuse the maker of not having scientific reports, but I think any electrochemist would approve.

In particular, I'm not reviving trash, but using it during full charge AND moderate discharge purposes.

Keeping in mind that the negative plate never gets fully charged during normal cc/cv routines, instead of me manually going into overcharge with a programmable bench supply, the PP-12-L model is used instead to help keep the negative plates *passivation layer* open. This might alleviate my use of the inherently risky knife-edge of manual over-charging.

I almost hate to admit using it, since the field is so full of charlatans. I stuck to the original maker, who actually DOES have reputable studies behind it.

It just leaves me to wonder - what results if any could be obtained from an already 20 year old off the shelf product if placed upon an UltraBattery? In both charge AND discharge? Dunno, maybe it would innefective on carbon. Hard to tell since an Ultrabattery is not available to us *small* solar guys afaik.

I know that most of this is rhetorical really, so sorry about that. I know that none of this is new but had to get it off my chest.

Crossing the event horizon now...

[inetdog]

Crossing the event horizon now...

You do know that from your point of view it will take an infinite amount of time to even reach the event horizon?

[PNjunction]

Heh, don't I know it!

It is such a dangerous subject to approach. Staying scientific about it is very hard without being vendor specific.

I guess I'll say it - BECAUSE of that independent study, and the reputation of the Professor who did it, it comes from the original maker- PulseTech. If it didn't exist, or had a nobody behind it, I wouldn't have even mentioned it. The FULL version of the report is what is truly worth looking at. I'm using a bit more modern version PP-12-L.

Sulfation is the boogeyman of batteries, and is the only thing a consumer can relate to. Dealing with it at the PCL level as the REAL benefit is much harder to explain. Not to mention positive plate corrosion reduction, but consumers can't relate to that.

"Bob, it looks like your battery is suffering from PCL 2 and 3. Might want to look into the passivation layer." Huh?

At any rate, the other question about normal pwm waveforms vs pure dc charging (clean with no ripple) might be something to take into account to see if that skews results any.

[PNjunction]

Ugh.. allowing me to hang myself right.

I'll try to summarize to the best of my layman's knowledge of what's going on:

1) Unwanted secondary chemical reactions can create a progressively insulating layer between electrolyte and electrodes. Lithium also has a passivating layer.

A great intro to this for lithium from Professor Jeff Dahn of Dalhousie Uni can be found here:

https://www.youtube.com/watch?v=pxP0Cu00sZs

2) The low-voltage triangle wave of the Pulsetech does NOT *directly* affect lead-sulfate crystals! What it does seem to do is somehow manipulate this insulating unwanted secondary-reaction passivation layer. Some have called it "micro-stirring".

(Note - this is how to tell the charlatans from the real thing - those who are trying to find the resonant frequency of crystals, specific rf frequencies, sound waves or other nonsense to *directly* affect sulfation are coming at it from the wrong direction - looking at the effect and not the cause so to speak, other than mere insufficient charging.)

3) That passivation layer, once manipulated, seems to allow for re-establishment of contact with sulfate crystals that were once insulated from the active material, and now allows for charging to complete the reaction back to lead - at least the stuff that hasn't hardened into concrete. Most commonly seen as removing whitish lead-sulfate-precipitate on the surface.

4) It also performs this process on any lead-sulfate within the pores of the plate's active material. Usually a change in morphology of the active surface can be seen as well.

5) This morphology change can benefit batteries where the plates have not been fully formed, perhaps inexpensive ones that have plates formed by the "one shot" pre-built process, rather than the more exacting individual plate "tank formation" process.

6) Along with the reduction in sulfate, this manipulation of the um, layer of junk in between the electrolyte and active material allows for a faster ion transition, or diffusion. Improves the DCA or charge/discharge rate as alabc puts it.

This improvement in DCA, or diffusion takes place on both charge AND discharge, so ideally the pulse unit should be on all the time. Yeah, the PP-12-L is a stand-alone unit that does draw a miniscule amount of current so you have to charge once in awhile or provide some other means of power. But this is kindergarten information, so no more needed on that.

7) Since the battery is now running in a more efficient state, the battery will spend less overall time in the higher-voltage absorb state. Less time overall here means less positive plate corrosion. There may be other chemical reactions going on to either improve or slow down the positive plate corrosion, but by now my head is sulfated.

My hope is that by running in a very efficient state, what is known as the "knife-edge" between positive plate corrosion and negative plate sulfation may be relaxed a bit, and I won't have to spend a lot of time with "refreshing charges", or extended 14.4v CV past the usual normal limits for an agm on a regular basis.

8) Many copycats of the Pulsetch abound, each with a differing waveform. Problem is, the REAL way to engineer it would be to study the effects it has on the intermediary layer of junk, rather than relying on secondary results, such as sulfation. So, a waveform that might seem to total magic to sulfation, may have a totally undesired side effect of actually *aggravating* positive plate corrosion!

In other word, just "winging it" with some random waveform is not reliable enough to warrant serious use, unless you are a huckster. PROFESSIONAL studies of your waveform must be passed and published from a verifiable and reliable entity. Patents alone are not enough. To my knowledge, only Pulsetech has supplied the most professional reports.

9) AND, from Professor Dahn's lab, we know that just quickly doing a repetetive quick cycle hammering of batteries does NOT provide real world calendrical aging data, despite how good your lab is conventionally. To do it right within a resonable amount of time to make and qualify needed improvements, you need something on the order of the Dalhousie University battery measurement lab. Really.

... microphone drop! ...

[PNjunction]

None of this is really new ..

What I wanted to say here is that none of this is new about PCL modes 1/2/3, especially to the members of the ALABC for sure.

Without trying to rewrite the whole history of their experiments very poorly, I recommend others interested to seek out non-marketing scientific materials for this study.

One word or warning is don't try to read too much into my observations about the pulsetch pulsing. Don't go overboard thinking that it can turn a high-quality lead-calcium agm into a pure-lead-tin agm!

I can attest to improved functionality with both lead-calcium and pure-lead batteries, but one can only take anecdotal anonymous internet data so far. One must do their OWN testing as well, and not jump to conclusions either pro or con. Keep your head straight.

One area that is also fraught with danger is the subject of the electrolyte itself!

We witness the change from lead-calcium to pure-lead-tin to combat primarily PCL 1 and 2. Merely switching to a non-calcium and tightly compressed agm format helped in that regard. But then, we see a switch back from pure-lead to a substitution of calcium / graphite and carbon in various forms. Some successful, some not so. Of course this is an oversimplification as PCL 3 requires, no matter the chemistry, proper charging / maintenance no matter what. See what the ALABC has already done in this regard.

The thing is, there is a whole lot of "pre-competetive" work being done with the active materials. But not much has been said about the electrolyte itself. Is it time for a change or modification? Could this be the secret competetive sauce?

Clearly as in the case of lithium, while active materials are being improved, it is the additional proprietary substances added to the electrolyte which are the primary movers. See Prof. Jeff Dahn's lab at Dalhousie U for more info.

So what I see as being the big problem is that with lead-acid, either flooded or VRLA, is that nobody can improve the electrolyte without fear of discovery by competitors, since it is so mechanically easy to isolate. Thus we are left to concentrate solely on the active plate-materials themselves without taking into account the performance improvements that can come from modifying the electrolyte specifically to match/improve the active material chemistry under test.

[PNjunction]

East Penn / Deka teasing consumers about UltraBattery?

This is the kind of marketing that drives me crazy. For now, the UltraBattery seems destined solely for black-boxed industrial solutions, the typical grid-stabilization industrial crowd, or for cars not really for sale to the public, or perhaps at most, a half-hearted handful of CARB models. We've seen plenty of those come and go.

http://www.alabc.org/publications/ad...energy-storage

Man, that sure looks a lot like the powersports East Penn / Deka Intimidator shells that I know and love:

http://www.eastpennmanufacturing.com...Flyer-0278.pdf

So the big question is, "WHEN WILL I SEE THIS IN MY LOCAL AUTOZONE store? Is that little windfarm really using a bank of powersports versions of the Ultrabattery?

My own 2011 Honda insight is starting to tick over 100K miles and will be needing a replacement battery soon. Will I be able to ask my Honda tech department to get me the ultra-battery version of it, or is it just vaporware?

Lithium's popularity is partially due to it being everywhere, from shirt-pocket to large industrial setups.

If you want Pb to compete better with lithium, you need to BRING IT TO THE COMMON MAN, DIRECTLY (ie, Autozone, Oreilly and the like) and not just provide it solely to industrial customers. If you try to stick to a black-box proprietary customer base, well then good luck with all the rest of the competition out there in that segment of the market.

I know it is primarily designed for HRPSoC, but just imagine what kind of smiles you would bring to the guy who knows how to charge and maintain them properly in the first place? You could have a near cult following, but to do that you need to bring it to the common man soon, lest we lose interest and look elsewhere to get our lead-acid fix.

[PNjunction]

ALABC - enough testing already with my money!

Much of the research over the past has been done with DOE funding. But guess who funds the DOE? WE DO with our taxes - many people think that funding just comes out of thin air and not realize it comes directly from their pocketbook.

My plea is to learn from the past, stop your competetive bickering (even in this so-called pre-competetive period), and actually bring something to market to benefit the common man. Directly.

You know who almost stopped Henry Ford in 1903? The ALAM (Association of Licensed Automobile Manufacturers):

http://www.bpmlegal.com/wselden.html

Of course I also don't need to mention the recent NiMH patent encumbrance which to this day prevents me from making an efficient NiMH battery with the fewest cells possible. I'm stuck with a nightmare of multi-multi-cell packs and all the issues that entails trying to buy anything larger then 10ah ....

https://en.wikipedia.org/wiki/Patent_encumbrance_of_large_automotive_NiMH_batteries

I kind of don't understand the whole pre-competetive thing from a common-man sales demographic. Would the introduction of the lead calcium / carbon UltraBattery hurt retail sales of pure-lead products? Is that why I don't see this revolutionary battery on the shelves or one-click away?

I've indirectly funded your battery research for EV / Renewable energy for years. How about throwing the common man a bone and putting a product on OUR shelves?

[PNjunction]

Historical documents lead me to believe I have answered my own question. Or more accurately, again ask the ALABC if their tests are conducted using pure-dc, or a pwm modulated waveform for their charging?

Since 99.9% of the solar users in the world rely on PWM, (either directly with inexpensive controllers once they reach CV, or with MPPT who also use PWM during the CV phase), what effect does this waveform have on Pb batteries, in regards to the passivation layer? Something that lithium has too, albeit different form, but the end result is the unwanted secondary reaction of the chemical process. (Prof Jeffery Dahn's win series on lithium was instrumental to me, but back to Pb..)

Long ago when the line of Morningstar pwm solar controllers came out, they touted the benefits of it - namely desulphation and increased charge acceptance. You can see that claim today in the marketing white paper entitled "Why PWM" here:

http://support.morningstarcorp.com/w...anuary2000.pdf

They even reference materials from another well-regarded battery organization, CSIRO to back it up.

What I find interesting now that I am reading their materials in depth, their pwm waveform ALSO includes a negative-going pulse, which is a component of "burp" or "reflex" charging which for the most part seems to have claims that are widely dismissed by the electrochemical community. Such as the reduction of hydrogen bubbling, or at least the precursor to it. At the very least, while these claims since about 1971 testing, most of what I read in the community says at the very best it is benign.

The point here isn't to get into the decades old burp-charging or reflex argument however, but it was because of this widely dismissed burp charge that I looked into just the positive-going pulses in the first place!

Here is what I find very interesting:

If you go into the wayback machine of 1995 or so and start looking up patents, you'll find that Morningstar goes into great length countering the claims of the prior-art of Carl E. Gali, of "solargizer", which today is more easily recognized as PulseTech. The Morningstar patent emphasizes their pwm tech is more about voltage and current control, with a nod to equalizing voltages to reduce sulfation.

BUT turn the page to Morningstar's "Why PWM" white paper which appeared a few years later and suddenly here is desulfation, along with a host of other benefits!!

THE BIG ISSUE to keep in mind is what type of "pulse" charging are we talking about?

1) Is it just a low-voltage high frequency triangular waveform superimposed on a dc bias that deals primarily with the interface layer reduction, ala PulseTech?

2) Or is it the type of pulse charging which is high-current, high-voltage, dv/dt and other methods for termination, like the NREL studies did on Optimas 16 years or so ago?

3) Or, the primary charging method of voltage and current control to be far superior than linear or on/off regulators, aka Morningstar. At least originally from their early patent. But now, we seem to include the very things that Pulsetch / Gali proposed (and eventually got LAB tested from a known reputable Professor) shortly thereafter.

Apples and oranges, which marketing (and diy'ers) try to exploit to the fullest with their sales demographic not knowing the difference!

Readers will note that this is the same timeframe that PulseTech actually submitted their device to independent testing, primarily from Professor Tadeusz Malinski which includes X-ray diffraction, electron microscopy and other data, PUBLISHED for all to see. The only thing I see from Morningstar are claims.

http://xtremecharge.com/themes/Xtrem...inski_Full.pdf

I own several Morningstar solar controllers, and like them very much - they work very well, although I have NOTHING like x-ray diffraction or electron microscopy from them that Pulsetech provides. Makes me wonder since my own Pulsetch chargers also work very very well. So what's up there?

I actually got the pulsetch partly because of this appearing to be a bad case of "Methinks the lady doth protest too much". I have no comment on anything other than Pulsetech, namely all the other products out there that misread the original Gali patent and went wild with guesswork with other random waveforms.

Despite all this, we return to the bigger question for ALABC:

1) Again, are you using pure-dc or a pwm waveform of your own during testing? And if so, what are the details of that waveform?

2) Since I can't get a hold of any of these advanced battery products as an average consumer, should I just continue on with my own PulseTech units (stand-alone PP-12-L models) with my agm's to force my "standard" agm's (lead-calcium AND pure-leads / tppl) to get some of those same characteristics such as enhanced resistance to PSOC, better charge acceptance, reduction of PCL modes 1,2, and 3 with common consumer outlet agm's?

A general fog of marketing has clouded the issue for many decades understandably, especially with all the benchtop hacks which didn't understand electrochemisty - or at least were never able to publish laboratory studies proving their claims. To this day, only Pulsetech seems to have done so, so I plan on to continue using them with my VRLA's.

Bring an Ultra-Battery to my neighborhood store, and perhaps I'll have a reason to stop using them.

[PNjunction]

What about discharge?

Putting aside sulfation for the moment, the material contained inside the FULL report by Prof Tadeusz Malinski for Pulsetech showed not only increased charge acceptance, but also the inverse - better discharge paramaters too. THAT was seemingly the most beneficial data - desulfation was a byproduct!

Which makes me wonder if ANY alabc testing was done with pulsing during DIScharge? That is, the load may not have to be pulse-discharged, but a pulse waveform bias introduced during the normal discharge of the standard loads.

Again, Pulsetch is the ONLY (and seemingly original one that everyone copied differently) that provided real-world testing data - not just marketing hype.

Had it not been for the valid report, I like most others dismissed pulsing out of hand. I think there is something to it, the original low-voltage triangular waveform that is, for both charge AND discharge.

Heh, too much of a hot-potato subject I suppose.