lithium shipping hazmat fees

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Re: lithium shipping hazmat fees

Post by busted_bike » Dec 06 2010 9:03am

As I recall, about 2/3 of the energy released for virtually any lithium chemistry cell on ignition is due to combustion of the electrolyte. So even a completely drained LiFeP04 cell represents a potential fire hazard under the right circumstances. So I'm with Jeremy on this one.

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Jeremy Harris   10 GW

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Re: lithium shipping hazmat fees

Post by Jeremy Harris » Dec 06 2010 9:23am

BMI wrote:You are full of absolute BS Jeremy! Are you willing to put your money where your mouth is?
If you can explain how I can download to this forum for all to see a 5MB file of crash lab testing /and CE testing of LiFeTech batteries I will prove to you how wrong you are.
Go and very carefully READ what I've written, rather than continue to try and promote your product in used-car-salesman mode. I am talking about this topic, which is HAZMAT, not some more of your advertising spiel about mechanical robustness or whatever, which has no bearing at all on this specific issue. Lithium containing products potentially fall into HAZMAT category 4, flammable solids, depending on the quantity involved. They may even end up being in category 9 (which is a pain) if the information provided by the shipper can't prove they belong in 4. Yours are no different to any other in this regard.

We're not talking about mechanical robustness, crash-worthiness, or relative safety when being charged, we're talking HAZMAT, specifically, flammability. Is that clear?

The issue that vexes air transport regulators is the difficulty in suppressing a lithium fire, as I've now repeated a couple of times in this thread. Any product that contains significant amounts of lithium presents a potential fire hazard, in as much as conventional aircraft fire suppressant systems can't adequately deal with flammable solids fires of this type. There's also the issue of the flammable organic solvents used in lithium cells, although these have been proven to be suppressed by conventional Halon fire suppressant systems fitted to some cargo aircraft.

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Re: lithium shipping hazmat fees

Post by texaspyro » Dec 06 2010 11:57am

Almost all rechargeable lithium batteries these days do NOT use metallic litihium. The only time you get metallic lithium in these batteries is when it plates out of the chemistry due to radically improper charging.

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Re: lithium shipping hazmat fees

Post by Andje » Dec 06 2010 12:05pm

LiFeTech batteries will absolutely not catch on fire unless you actually put them into an existing fire
We're not talking about mechanical robustness, crash-worthiness, or relative safety when being charged, we're talking HAZMAT, specifically, flammability. Is that clear?
... i just feel like your on the same page staring at each other through a thick haze ...

If this turns into a duel, pistols at ten paces, and my money is on Jeremy. I also bet Jeremy could make one of LB's batts catch fire, but i'm only needling because i also hate fear mongering :(. There's enough ignorance doing harm out there already.
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Re: lithium shipping hazmat fees

Post by The Mighty Volt » Dec 06 2010 12:26pm

katou wrote:In Canada, all lithium batteries must be shipped ground and be identified as such. There are no other restrictions on them.

I called Canada post and got referred to their special regulatory group, and they explained the ground shipping restrictions.

My point is that I went to the source (for Canada) and got the info straight from the horse.

Call them yourself if you want, it's not a big deal to them. I checked this out before I sent batteries to Ireland, Texas, Boston and Florida.

No problems.

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Re: lithium shipping hazmat fees

Post by Jeremy Harris » Dec 06 2010 12:38pm

texaspyro wrote:Almost all rechargeable lithium batteries these days do NOT use metallic litihium. The only time you get metallic lithium in these batteries is when it plates out of the chemistry due to radically improper charging.
True, but this doesn't abate the fire hazard. As I understand it, the way that the reactions take place when exposed to fire is that the organic solvents in the electrolyte burn quite readily, then the lithium oxide, polyanion or spinel can convert to metallic lithium via reduction under heat (the burning electrolyte having created a reducing atmosphere adjacent to the electrodes). The next stage is the metallic lithium fire, which is the thing that so vexes air transport regulators. The regs currently require shippers to give an 'equivalent metallic lithium' content, I believe, and they base the risk assessment on that, using an assumption that the lithium content will become metallic in the event of a fire.

We have some evidence of way that LiFePO4 undergoes this reaction from Greg Fordyce's fire on his converted Fiat 126. The cause may not have been the cells, which were being charged overnight at the time, but there's no way for sure of knowing what initiated the fire now. What we do know is that there was a fierce blaze when the batteries went up, hot enough to melt the glass in the door, indicating that there was almost certainly metallic lithium burning in the cells at some point. Greg has confirmed that the LiFePO4 cells were the 'hot spot' in the blaze, but the damage was so severe that there's no way of knowing the actual cause, although he suspected that it was either a fault in his home-made BMS or an internal short in one of the cells. The pack was fully charged and in the balance phase when it went up, so there was a lot of stored energy available to make a short circuit a viable way of starting the fire.

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Re: lithium shipping hazmat fees

Post by Jeremy Harris » Dec 06 2010 12:43pm

Andje wrote:
LiFeTech batteries will absolutely not catch on fire unless you actually put them into an existing fire
We're not talking about mechanical robustness, crash-worthiness, or relative safety when being charged, we're talking HAZMAT, specifically, flammability. Is that clear?
... i just feel like your on the same page staring at each other through a thick haze ...

If this turns into a duel, pistols at ten paces, and my money is on Jeremy. I also bet Jeremy could make one of LB's batts catch fire, but i'm only needling because i also hate fear mongering :(. There's enough ignorance doing harm out there already.
Exactly. The issue under debate was whether or not LiFePO4 cells are a flammable, which is simply a matter of basic chemistry. Armin was doing his usual trick of trying to exploit an unrelated thread as a means of advertising his particular product, not for the first time.

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Re: lithium shipping hazmat fees

Post by PedalingBiped » Dec 06 2010 12:48pm

I'm with Jeremy. The position of the containers tells me they weren't being treated as hazmat.
Also, UPS is air freight. Try shipping ground with a LTL, the batteries don't even raise eyebrows cause there only class 9,(misc). An entire trailer can be full of batteries without placarding.

as far as employees purposely damaging freight, with 1000's of packages going by, when do they have the time?

You can roughly equate wages with IQ. I too have seen the results when a liftgate was too small for a crate so the driver pushed it off. made a big crater in the blacktop.

PS I'm one of those drivers that deliver your freight and think about my quality as being normal, not exceptional.
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Re: lithium shipping hazmat fees

Post by texaspyro » Dec 06 2010 2:31pm

Jeremy Harris wrote:True, but this doesn't abate the fire hazard. As I understand it, the way that the reactions take place when exposed to fire is that the organic solvents in the electrolyte burn quite readily, then the lithium oxide, polyanion or spinel can convert to metallic lithium via reduction under heat (the burning electrolyte having created a reducing atmosphere adjacent to the electrodes). The next stage is the metallic lithium fire, which is the thing that so vexes air transport regulators. The regs currently require shippers to give an 'equivalent metallic lithium' content, I believe, and they base the risk assessment on that, using an assumption that the lithium content will become metallic in the event of a fire.
I think that once the electrolyte torches off, any lithium burning is just icing on the cake.

I also think that their main bitch with lithium (metallic) is what happens when Fire Marshall Bill takes a wikileak on it... just a little less interesting than sodium. But then I can ship my cesium beam oscillators with nothing more than a sticker on the box (granted the 6+ grams of metallic cesium is behind several layers of high vacuum shielding... but shippers are oh, so creative about breaching even the most unbreachable packaging)

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Re: lithium shipping hazmat fees

Post by Jeremy Harris » Dec 06 2010 3:00pm

texaspyro wrote:I think that once the electrolyte torches off, any lithium burning is just icing on the cake.




I'm not so sure. The evidence from Greg Fordyce's Fiat EV LiFePO4 fire shows that very high temperatures were reached in areas adjacent to the battery pack that went up, high enough to have melted the glass in a window and the alloy of the gearbox. The temperatures reached were much higher than those seen when ordinary ICE cars catch fire, I believe, which fits with this being a lithium fire, rather than just the small quantity of organic solvent in the electrolyte.
texaspyro wrote:I also think that their main bitch with lithium (metallic) is what happens when Fire Marshall Bill takes a wikileak on it... just a little less interesting than sodium. But then I can ship my cesium beam oscillators with nothing more than a sticker on the box (granted the 6+ grams of metallic cesium is behind several layers of high vacuum shielding... but shippers are oh, so creative about breaching even the most unbreachable packaging)
The fire suppressant systems in cargo aircraft (when fitted) use Halon, rather than liquids. Class 4 powder suppressants aren't generally safe for use on aircraft in flight, neither are aqueous fire extinguishing agents, although both would be used in the event of a ground fire.

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Re: lithium shipping hazmat fees

Post by pdf » Dec 06 2010 3:11pm

I'm pretty sure any Li chemistry battery of any significant size (that is, larger than you would use in your average camera) cannot be shippped via air in the US. I was reading the regulations for this just last month (which by the way are pretty long and complicated). So charging extra for shipping Li batteries via UPS due to expected fire hazard via air transport in the US would serve no point.

From a practical point, I just mailed a 15 A-hr LiFePO4 battery UPS Friday. I was completely clear about what I was shipping and the guy at the shipping office examined the battery, which had the battery chemistry labeled on it. He called someone at UPS wh supposedly knew the regulations and was told all it needed was a specific label and that it could not be shipped air freight, which I already knew. There was no surcharge of any kind.

Anyway, that is my understanding; no air shipping of lithium batteries of ebike size in the US. That was certainly the understanding of UPS. As to whether or not a particular battery chemistry will burn, there is a theoretical and experimental approach. In chemistry, the theory often comes after the experiment. Sodium reacts violently with water as a metal and not at all as a salt. I don't know about the form of lithium in batteries. Presumably, someone has actually tried to burn one. Ask that person what happened.
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Re: lithium shipping hazmat fees

Post by Jeremy Harris » Dec 06 2010 3:16pm

pdf wrote:Sodium reacts violently with water as a metal and not at all as a salt. I don't know about the form of lithium in batteries. Presumably, someone has actually tried to burn one. Ask that person what happened.
The lithium in cells is either an oxide, polyanion or spinel. In the case of LiFePO4 it's a polyanion.

This is the consequence of a LiFePO4 pack catching fire during charging:

Image

I think it probably falls into the category of an 'experiment' that proved that they do burn, quite violently. This car was an EV, and had no fuel onboard other than the battery pack and the normal flammable interior materials.

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Re: lithium shipping hazmat fees

Post by oldpiper » Dec 06 2010 3:57pm

OK, a little bit of chemistry:

The lithium in a battery is primarily going to be elemental lithium (Li metal atoms, whether or not they are touching each other to make an actual macroscopically-observable "piece" of lithium) when the battery is charged up. Discharging takes away an electron from those atoms to form lithium ions (Li+), with a release of energy. This energy is hopefully seen as Watts, when the electrons in the circuit move from one end to the other, turning your motor, etc. Charging reconverts the Li+ back to Li, giving you your energy back for the next run.

As long as the two sides if the battery cell are where they are supposed to be and are separated by an appropriate membrane (one that will not decompose), everything is fine. The problem comes when the cell walls or the cell membrane are breached. If the cell walls are breached, the Li atoms will react with oxygen or water vapor in the air (or liquid water) as they ooze out with the electrolyte, fizzing, heating things up a bit, and producing a caustic crud where the insides have escaped the battery. In extreme cases, the hydrogen gas produced could also produce a hazard, if trapped inside the battery pack (or the shrink-wrap) and a spark occurs from somewhere. This last part is not too likely, as the Li generally escapes the cell slowly.

If the membrane separating the two half-cells is breached, that's another matter. This can easily lead to an internal short-circuit of the battery since the electrolyte is conductive, and a LOT of energy (essentially all the energy that the battery has stored) can be released in a very short time within a very small volume. Now, you have an extreme amount of heat with nothing to do but catch any flammable material inside on fire, damaging inside and outside compartments further, leading to more heat, possibly spreading damage to the next cell over, causing it to catch on fire, and so forth.

This is what happened to the Sony computer batteries that caught on fire and made the national news - when a Li battery is recharged, the Li atoms don't always reform exactly where they came from and small needles, called dendrites, form. Sometimes these dendrites actually grow long enough to pierce the membrane separating the half-cells, and if this happens enough, Boom. That is one big reason why batteries cannot be charged too awful fast, fast charging leads to more dendrite growth, although some dendrite growth takes place every time the batteries are charged. This is also one reason why there is a lot of research going into electrodes using things like carbon nanotubes to isolate the individual Li atoms, so dendrite growth can be prevented, but not separate them too far from each other, or you lose energy density.

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Re: lithium shipping hazmat fees

Post by katou » Dec 06 2010 4:01pm

I'm not sure who's right, but I can surely see who has more investment in BEING right.

We're supposed to be learning here, not grinding axes.

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Re: lithium shipping hazmat fees

Post by oldpiper » Dec 06 2010 4:46pm

pdf wrote: As to whether or not a particular battery chemistry will burn, there is a theoretical and experimental approach. In chemistry, the theory often comes after the experiment.
Just a little clarification here: In chemistry (and all science), the theory ALWAYS comes after the experiment. The theory is an explanation of what happened in the experiment which is consistent with all of the facts, in order to guide further experimentation. Without the experiment, there is no theory, in the scientific meaning of the word (as opposed to police/detective shows).

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Re: lithium shipping hazmat fees

Post by oldpiper » Dec 06 2010 4:52pm

katou wrote:I'm not sure who's right, but I can surely see who has more investment in BEING right.

We're supposed to be learning here, not grinding axes.

Katou
I don't see any axe-grinding here. I see Jeremy advising the readers of this forum not to believe in magic, if the magic contradicts rational thought.

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Re: lithium shipping hazmat fees

Post by Lessss » Dec 06 2010 5:58pm

Given a high enough temperature even concrete will burn.
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Re: lithium shipping hazmat fees

Post by oldpiper » Dec 06 2010 6:03pm

Lessss wrote:Given a high enough temperature even concrete will burn.
Uh, no, sorry. If it doesn't contain dirt or other trash picked up from the mixing site (not supposed to be in concrete), everything in concrete is fully oxidized (burnt).

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Re: lithium shipping hazmat fees

Post by texaspyro » Dec 06 2010 6:09pm

If the interior of that car was padded with foam rubber, it was basically padded with squishy gasoline. That stuff can burn unbelievably hot. I know a guy that uses it as rocket fuel (with N2O as an oxidizer)

Also, I don't know how big his pack was, or what its lithium equivalent was, but I have burned several pounds of magnesium shavings. Not particularly exciting, the equivalent weight in foam rubber would do more damage (spreads a lot better).

I have also see what happens when the Las Vegas fire department attempts to put out a fire in a building containing several hundred pounds of very finely powdered magnesium with water... much more entertaining. A good time was had by a gaggle of lawyers.
Last edited by texaspyro on Dec 06 2010 6:19pm, edited 1 time in total.

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Re: lithium shipping hazmat fees

Post by pdf » Dec 06 2010 6:11pm

So there are two types of fire hazards that seem to be discussed here; the oxidation of lithium metal and the burning of whatever else the battery is made out of.

The difference, presumably, would be that in the case of the car in the picture, you'd probably survive if it was the non-metal material that caught on fire and you got out of the car but the heat from direct oxidation of lithium metal would, presumably, be much hotter and the reaction much faster. In which case, you might be toast, depending on how much lithium there was in the battery.

The original question, was, "Is it dangerous to ship Li batteries of various chemistries?", or maybe "Is it more dangerous than other battery chemistries?" I guess if the car in the picture is an example of what can much more easily happen with a lithium battery, it is probably irrelevent what the nature of the fire was; if it is on an airplane, the plane is coming down. Seems like it might make a difference for surface shipping however. UPS seems to be OK with surface shipping. The USPS is not, however. I think you still can't ship a lithium battery, except those in consumer electronics, via USPS.
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Re: lithium shipping hazmat fees

Post by katou » Dec 06 2010 6:19pm

Oldpiper, you misunderstand who that was meant for.

The pointy bit of my prose was directed at those with something to sell, certainly not Jeremy. Although, I do think he should make up a batch of those "gas gauges" for sale.

I am (and have been since joining) a huge fan of Jeremy, and I always read what he has to say very carefully. I find his posts to be informative and very balanced.

Katou

ps personally I think their disagreement stems from the fact that some lithium chemistries are safer than others (BMI's point) regardless of the fact that they all contain lithium which is always flammable (Jeremy's point) Or, I could be completely wrong.

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Re: lithium shipping hazmat fees

Post by katou » Dec 06 2010 6:22pm

I've shipped several small orders (around 20 cells) into the US using USPS with the boxes clearly labeled "cordless tool lithium batteries".

So, de facto, they do ship them.

I'd like to hear the "de jure" USPS policy on that, can one of you US'ers give them a call for me? It's long distance from here.

Katou

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Re: lithium shipping hazmat fees

Post by oldpiper » Dec 06 2010 6:23pm

OK.

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Re: lithium shipping hazmat fees

Post by pdf » Dec 06 2010 8:53pm

Well, the regulation appears to be less than 8 g per "battery" of lithium equivalent. Quoting from the USPS website:

" 622.52 Secondary Lithium-ion (Rechargeable) Cells and Batteries
Small consumer-type lithium-ion cells and batteries such as those used to power cell phones and laptop computers are mailable with the following restrictions:

Individual cells or batteries are mailable when the cells or batteries are properly packed with or properly installed in the equipment they operate.
Each cell must contain no more than 1.5 g of equivalent lithium content per cell.
Each battery must contain no more than 8.0 g aggregate quantity of equivalent lithium content per battery.
Each cell or battery must meet the requirements of each test in the
UN Manual of Tests and Criteria, Part III, and subsection 38.3 as referenced in the DOT’s hazardous materials regulation at
49 CFR 171.7.
Individual mailpieces must not contain more than three batteries. "

I have seen reference to 8 g. of lithium being on the order of 100 W-hrs on the FedEx web site, although it seems that might depend on the battery design(?) I have a 36v 15 Ahr battery so I assume I can't ship that via USPS. I just shipped it Friday via UPS, no problem.
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Re: lithium shipping hazmat fees

Post by BMI » Dec 06 2010 8:57pm

Jeremy Harris wrote: The regs currently require shippers to give an 'equivalent metallic lithium' content, I believe, and they base the risk assessment on that, using an assumption that the lithium content will become metallic in the event of a fire.

Jeremy
Please explain how a LiFeTech LiFePO4 battery which has "ZERO GRAMS EQUIVALENT LITHIUM" metal can catch on fire??
I have attached the MSDS as proof.

To use your own words- " using an assumption that the lithium content will become metallic in the event of a fire".
I am looking forward to your explanation of how a battery which CANNOT produce free lithium metal EVEN IN A FIRE can catch on fire due to free lithium being released due to the heat of a fire.
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