Inhaled vapors from battery!!!

[LED61]

I had a very scary situation last night. I want to post it here so that fellow CPF´rs will avoid it and the dangerous potential it has.

I have been savoring of my soon to arrive SF M6. Knowing of the high current demand, I have been all over Newbie´s, Silverfox´s and LunarModule´s threads to learn as much as possible about batteries and avoid dangerous pitfalls. It makes me angry that I was so stupid so as to have this happen to me after all this research to avoid this very thing. Nonetheless, it happened and I´d like to tell all about it.

Last night, at around 9 PM., I was unpacking a new shipment of Sanyo made in China CR 123 primary Lithium batteries, 20 of them to be exact, that came neatly packed in plastic sealed bags. They all looked good to me, as I would test them soon with my new ZTS tester before use. Then, accidentally, I dropped one of them from about 4 feet. The impact is what I would consider mild and I was not alarmed, nonetheless, a strange but non- repulsive smell was felt. I looked at the battery, and out of instinct and without much thought picked it up, pulled the positive end with the vent holes up close to my nose and inhaled to see if the battery was venting!! (how stupid could I have been!!, after all the research to avoid this very thing) AAGGHH!! I immediately placed the battery outside and swore this would be one battery I would not be using in the flashlight. I did this too because, after all, maybe only a battery explosion would be dangerous right ?? I forgot about the incident and headed upstairs to watch a movie on TV.

Then, about 20 minutes later, it hit me. Surprisingly and out of the blue, I started coughing violently, felt a severe shortness of breath along with chest pain. My arms and legs started to weaken on me and go "cold". A rush of panic set on me and I immediately linked the episode to a reaction of the inhalation of vapors from the dropped battery.

I woke up the wife and my 18 year old son, and briefed her on what was happening to me and where I thought it was coming from. We agreed to review LunarModule´s accident and do research on the internet on what to do. We also agreed to take an immediate drive to the emergency room at the hospital if the episode was to repeat itself or if there was any indication of a worsening of the situation. The episode itself was momentary, possibly around 20-30 seconds. We pullled an MSDS sheet here

http://www.bu.edu/es/labsafety/ESMSD...l#anchor888417

and pm´d a fellow CPF´r whom I hold in high regard for his experience and knowledge for guidance. Unfortunately, he was unavailable. OH wait, here it comes again!! another episode, this time though without the chest pain and not as severe as the first one. We rushed to the hospital, wife driving me, and into the emergency room and to the doctor. We explained what had happened, and surprisingly the doctor was well versed in this type of poisonous inhalation. He could relate to all the symptoms, and concluded I had inhaled dangerous Hydrofluoric acid vapor. The delayed reaction, he said, was due to the bloodstream absorbing the vapor and hence the shortness of breath, chest pain,and weak limbs. A third episode took place while in the emergency room but this time it was much less than the first or second episodes. It has been about 14 hours since this incident, I did not get much sleep last night but not because I felt bad, only very scared.

Hydrofluoric acid will, with a possible delayed effect, affect the nervous system, respiratory tract, lungs, and impair the cardiovascular system. Those effects are from inhalation only, more severe effects including weakening of the bones and a host of other things if ingested or from wounds such as LunarModules. i.e. skin contact.

WHAT I LEARNED AND MY DOCTOR SAID TO ME:

1) DO NOT DELAY a trip to the emergency room in the hospital if you have inhaled, ingested, or came into skin contact with Lithium battery venting.

2) Have someone else drive you to the hospital if possible. You could become quickly and without warning completely impaired. Oxygen and emergency treatment by qualified personel are your only chances of survival after cardiac arrest or if you are unable to breathe.

3) DO NOT ASSUME you are OK if you as much as think you´ve been exposed to battery fumes, EVEN IF the battery seems to be OK and explosions are not a requisite.

4) Keep handy antidote in the form of calcium gluconate saline solution for inhalation or in gel form for skin cuts or burns. Intravenous solutions are a possibility and must be administered by hospital personnel.

This incident was very mild compared to other cases, but I assure you fellow CPF´rs, it is very scary and dangerous. A battery can start to vent if mishandled or dropped as in my case, it does not have to explode. It happened to a name brand chinese made CR123, it does not have to be a "cheap battery", this one cost me $2.00 a piece.
Don´t ever pull the vent holes in the positive end of the battery up close to your face or nose like I very stupidly did. If you suspect a battery is venting, just toss it aside.

Hopefully somebody else will benefit from this post.

[SilverFox]

Hello LED,

Glad to hear you are OK.

Tom

[greenLED]

Scary. Hope you continue to improve.

Thanks for the warning. Makes me think we should start storing these out of the reach of children...

[GreySave]

<<I looked at the battery, and out of instinct and without much thought picked it up, pulled the positive end with the vent holes up close to my nose and inhaled to see if the battery was venting!! (how stupid could I have been!!, after all the research to avoid this very thing)>>

LED61.....You were not being stupid. What you did was an almost instinctive reaction and something that any one of us might have done. The key to not taking the sniff test is situational awareness and taking the time to think about what has happened and how to correctly respond. That's not an easy thing to do. I know that I am guilty of doing things I would later consider as foolish, and I am sure many others here have done the same. Even trained responders can make a mistake or forget basic common sense at times. It is a part of being human. The important thing is to learn from a mistake, and you have done a great service by helping to educate all of us and by reinforcing the need for all of us to stop and think a moment before reacting to a similar situation.

Thank you for taking the time to pass along your experience and I wish you well.

[LED61]

Thanks guys I am Ok and it´s been about 16 hours already. hopefully I´ve seen the end of it with no aftermath.

Green LED, you are definitely right on. These batteries should be kept out of the reach of children. The warnings in the labels fall short of reality. I could not imagine a battery starting to vent just because I dropped it.

I have compared my surefire batteries, batterysttions, Sanyo´s with the OEM Duracelll that HDS shipped with my U60. I even compared that Duracell Ultra with an older Duracell and I can now appreciate the difference in the positive end. I´m not sure on the technicalities, maybe Tom or Newbie would educate us better on this but the thing is the Duracells appear to be much better construction with a metal lining on the positive end vrs. a plastic in the others. It is also apparently heavier.

[greenLED]

Grey, yeah, that instinct for sniffing things might've saved our ancestors from eating rotten food, but it can get us in trouble also. It's one of the first things you learn in lab safety: don't *ever* sniff directly out of a container!

LED, did the doctor tell you to keep watching for symptoms for a couple of days? Any estimates on how long it'll take for this to clear from your system? Other potential/longer term issues from the poisoning?

[RA40]

Scary!!!
I have various states of discharge 123's sitting on my desk. Brrr... Out to the grage they go for the recycling.

[cutlerylover]

I am really glad top hear you are ok...its stories like this that get me worried about using cr123's...I know that there are thousands of them being used every day but there is always that one time and thats all it takes...but then again if I really thought about it over the course of a day there are hundreds of things that could go wrong and have dangerous results...Its good to know stuff like this to try to prevent this from happening again...Now im paranoid...lol, seriously though Im glad to hear you are ok, and thank you very much for the information!

[prof]

First and most important, I'm glad you're ok. I understand sniffing--very natural reaction. I'm glad you had your wife drive you to the hospital--very good decision. Let us know how this progresses, please.

When I first joined CPF, I read a post where someone said that AA batteries were dead and 123s were the future. As a AA fan (actually a fan of standardizing items) that bugged me. Now, after not so many months, the shoe is on the other foot.

I also agree that the warning labels are not sufficient. I'm moving my small supply WAY out of my childrens' reach. My little boy is into everything these days...

[MrAl]

Hi there,

I wonder if this kind of thing can happen with Li-ion cells too?

[NiOOH]

Hi LED61.
First and most of all, glad to hear that you are OK and well.

Hydrofluoric acid is indeed a dangerous chemical, both as a fume and in liquid form. IMO, as a chemist it should not be allowed in consumer products.

[IsaacHayes]

Wow. At first I thought you were just talking about the "flashahol" smell that they normally have, sweet type smell. But then I read were you got sick! I guess that short drop was enough for a reaction! I hope you have no further symptoms!!!

Do li-ion rechargeables emit hydrofluoric acid as well when damaged? I know they can get hot/vent etc if abused, but I was wondering if they had the same toxic nasties or not?

[Size15's]

I hope you continue to recover and thank you for sharing your story and importantly the lessons learnt.

Al

[LED61]

Thank you all very much for the well wishes. It´s been around 19 hours already since this happened, and I only had a minor headache for about two hours this morning and right now mild pain on the left side of my rib cage. I´m constantly updating my doctor on this, but he seems more concerned about my lungs and mucous membranes in the respiratory tract. He does say however that exposure was apparently not in a high enough level to cause any severe damage. The biggest damage from severe inhalation would have been a pulmonary edema (water in the lungs).
How much of these minor discomforts have been caused by anxiety I don´t know. I am for sure anxious especially since most material safety data sheets do warn effects may be delayed for up to 24 hours.

green LED, the doctor did ask me to keep him posted as stated above. He said the liver will work hard to remove the toxins but he said that it would be as fast as the liver was capable. Obviously anyone with a history of Hepatitis (which I´ve not had) or any other liver disease or heavy drinkers or smokers would not fare very well in this. The trouble is you never know how much is too much for you. These effects are from inhalationonly thank God for that. If you were to get this stuff in your skin it would work its way into your bones and decalcify them and, unlike Hydrocloric acid, you would not notice an immediate burn in the skin. Mucous membranes are particularly sensitive to these vapors but it probably is not as big a problem as substance in the skin.

RA 40, be careful not to mix those batteries in multi cell applications

Cutlerylover, true on usage of the cells, but if you look closely most devices use Lithium in single cell applications like laptops, cell phones or cameras. Even then, Sony and Dell had millionaire recalls of laptop computers with defective batteries. The department of transportation has prohibited the carriage of Lithium cells aboard passenger aircraft. If you carried your flashlight using primaries aboard, you could very well be ordered to dispose of your cells if you wanted to take your flashlight aboard.

Mr.Al, according to Newbie´s battery tests Li ion rechargeables can be even more dangerous.

Al, thanks for your comments.

[Handlobraesing]

Originally Posted by LED61

If you carried your flashlight using primaries aboard, you could very well be ordered to dispose of your cells if you wanted to take your flashlight aboard.

I think they prohibit primary lithium as cargo on psgr flights, but it's alright as check-in/carry on luggage for the psgrs. If what you said was right, they'd make you pop out the CR2032 from your calculator, watch, laptop CMOS backup, car remote key, etc.

[KROMATICS]

Originally Posted by prof

When I first joined CPF, I read a post where someone said that AA batteries were dead and 123s were the future. As a AA fan (actually a fan of standardizing items) that bugged me. Now, after not so many months, the shoe is on the other foot.

They make lithium versions of AA batteries though so it's probably more about what's inside the battery than what size it is.

[LED61]

Originally Posted by Handlobraesing

I think they prohibit primary lithium as cargo on psgr flights, but it's alright as check-in/carry on luggage for the psgrs. If what you said was right, they'd make you pop out the CR2032 from your calculator, watch, laptop CMOS backup, car remote key, etc.

yes, you are actually correct, I did overstate the prohibition. Nonetheless, I found this interesting article

http://www.post-gazette.com/pg/06227/713653-96.stm

[David_Campen]

Do li-ion rechargeables emit hydrofluoric acid as well when damaged?

No, and neither do Lithium 123 primaries. I suspect that the adverse effects LED61 experienced were wholly psychosomatic.

[cutlerylover]

This question is for everyone...

How often does somethign like this happen with CR123's? I mean vent like that or explode when used? I know its rare but how rare? I just want to be cautious when using them...In what cases do poeple have problems with these batteries? Also would it be safer to store them inside or outside of the flashlight? I only need batteries in one light at a time...

[Sigman]

Thank you for that informative post! I NEVER get tired of safety education!! Indeed hoping your recovery continues!

[LED61]

Originally Posted by David_Campen

No, and neither do Lithium 123 primaries. I suspect that the adverse effects LED61 experienced were wholly psychosomatic.

David_Campen, you speak with an authoritative and assertive tone. I would like to know if your opinion is qualified or a mere "suspicion". The efects were real and unexpected. I had forgoten about the smell when it happened. If Hydrofluoric acid is not emmited by a lithium primary battery, would you mind telling me why the term is even mentioned in Duracell´s product safety sheet here?

http://www.duracell.com/procell/safety/pdf/2031_5.pdf

And you seem to contradict my doctor´s opinion on this also could it be he is wrong?

If you want to dismiss this fine, but I went through this and I can assure you I´ll do things differently next time.

[Art Vandelay]

Originally Posted by David_Campen

No, and neither do Lithium 123 primaries. I suspect that the adverse effects LED61 experienced were wholly psychosomatic.

Could you give a link to support your statement?

The information I have found leads me to believe that fumes from lithium batteries are dangerous. According to Energizer “Fire fighters should wear self-contained breathing apparatus. Burning lithium ion batteries can produce toxic fumes including HF, oxides of carbon, aluminum, lithium, copper, and cobalt. Volatile phosphorus pentafluoride may form at a temperature above 230° F.” http://data.energizer.com/PDFs/lithiumion_psds.pdf

[daveman]

Are there any potential substitutes for Hydroflouric Acid in lithion batteries?

I wonder if that substandard battery would have vented if it was already in a flashlight when dropped? Perhaps flashlights would serve as an adaquate cushion?

[David_Campen]

Originally Posted by daveman

Are there any potential substitutes for Hydroflouric Acid in lithion batteries?

I wonder if that substandard battery would have vented if it was already in a flashlight when dropped? Perhaps flashlights would serve as an adaquate cushion?

Hydrofluoric acid is _not_ used in Lion batteries.

[IsaacHayes]

It's not used, but it can be produced by burning of a primary.

Will burning of a li-ion create it as well?

[David_Campen]

Originally Posted by LED61

David_Campen, you speak with an authoritative and assertive tone. I would like to know if your opinion is qualified or a mere "suspicion". The efects were real and unexpected. I had forgoten about the smell when it happened. If Hydrofluoric acid is not emmited by a lithium primary battery, would you mind telling me why the term is even mentioned in Duracell´s product safety sheet here?

http://www.duracell.com/procell/safety/pdf/2031_5.pdf

Hydrofluoric acid is mentioned because if the battery _burns_ then one of the ingredients (the lithium trifluromethanesulfonate) can produce hydrofluoric acid. This only happens if the battery burns or "vents with flame". An analogous material would be the Teflon that is used to make non-stick cooking pans - if it burns it too will emit hydrofluoric acid.

In the data sheet, Section A is the list of materials in the battery and there is no mention of hydrofluoric acid in the battery.

And you seem to contradict my doctor´s opinion on this also could it be he is wrong?

What opinion are you talking about. If you mean this one:

3) DO NOT ASSUME you are OK if you as much as think you´ve been exposed to battery fumes, EVEN IF the battery seems to be OK and explosions are not a requisite.

Then I do disagree. This statement may be good advice for children but a mentally competent adult should be able to be a little more discriminating.

Oh, and as for the LunarModule iincident you do realize that it was most likely hoax.

If you want to dismiss this fine, but I went through this and I can assure you I´ll do things differently next time.

I agree with you here, you should probably stop using all Lithium batteries if you are going to have to run to the hospital everytime you get a whiff of flashahol.

[greenLED]

LED61 had this happen with primary *lithium* batteries, not rechargeable li-ion, in case that clarifies things for some people.

[NewBie]

Originally Posted by IsaacHayes

It's not used, but it can be produced by burning of a primary.

Will burning of a li-ion create it as well?

Of course it will.


Here is the MSDS sheet for a very common LG 18650 Li-Ion cell:
http://www.hp.com/hpinfo/globalcitiz...s_lg_liion.pdf

Molicel:
http://www.tek.com/Measurement/cgi-b...ameSet=service

Battery Space Li-Ion:
http://www.batteryspace.com/prod-specs/MSDSLiion.pdf

International Battery Li-Ion:
http://www.internationalbatteryinc.c...SDS_090105.pdf


As you get more recent MSDS sheets for Li-ion cells you will find the following standard disclaimer:

"Hydrofluoric Acid Exposure During Fire Fighting
This information is given for use of professional fire fighters responding to a warehouse fire where fire from other materials may incinerate battery. This section is provided solely in case of exposure, during fire fighting, to the combustion by-products. Hydrofluoric acid is not present in the product. Contact with battery causes none of the following symptoms.

Hydrofluoric acid is extremely corrosive. Contact with hydrogen fluoride fumes is to be avoided. Permissible exposure limit is 3 parts per million. In case of contact with hydrogen fluoride fumes, immediately leave the area and seek first aid and emergency medical attention. Symptoms may have delayed onset. Fluoride ions penetrate skin readily causing destruction of deep tissue layers and even bone. Fluoride interferes with nerve impulse conduction causing severe pain or absence of sensations. Immediately flush eyes or skin with water for at least 20 minutes to neutralize the acidity and remove some fluoride. Remove and destroy all contaminated clothing and permeable personal possessions. Before re-use, impermeable possessions should be soaked in benzalkonium chloride after washing. Following flushing of the affected areas, an iced aqueous solution of benzalkonium chloride or 2.5 % calcium gluconate gel should be applied to react with the fluoride ion. Compresses and wraps may be used for areas where immersion is not practical. Medicated dressing should be changed every 2 minutes. Exposure to hydrofluoric acid fumes sufficient to cause pain requires immediate hospitalization for monitoring for pulmonary edema."


So, where does this hydrofluoric acid come from?

Reviewing MSDS (Material Safety Data Sheet) for many of the cell layer separators (you can find a foot or two of it wrapped inside the Lithium Ion cell) show the generation of HF (Hydrogen Fluoride) and PFIB (Perfluoroisobutylene) from heat decomposition (such as a cell venting/explosion). HF, is a clear gas, will become Hydrofluoric Acid upon contact with even minute amounts of moisture (such as humidity). The United States Army Medical Research Institute of Chemical Defense has classified PFIB, also a clear gas, as a pulmonary agent.

Usually, items like this get glossed over in MSDS sheets.

Another item found in Lithium Ion cells that has flourine in it is the Lithium Hexafluorophosphate or LiPF6. This can also break down during venting/explosion and contribute to the generation of hydrofluoric acid.

A MSDS for LiPF6:
http://www.gfschemicals.com/Search/MSDS/2534MSDS.PDF


One company gives a better breakdown of what is in their product, instead of calling it proprietary:

Energizer Lithium Ion:

Acetylene Black (CAS# 1333-86-4) 0-2%
Biphenyl (CAS# 92-52-4) 0-15%
Diethyl Carbonate (CAS# 105-58-8) 0-15%
Dimethyl Carbonate (CAS# 616-38-6) 0-15%
Ethyl Methyl Carbonate (CAS# 623-53-0) 0-15%
Ethylene Carbonate (CAS# 96-49-1) 0-15%
Graphite (CAS# 7782-42-5) 7-22%
Lithium Cobalt Oxide (CAS# 12190-79-3) 15-30%
Lithium Hexafluorophosphate (CAS# 21324-40-3) 0-5%
Lithium Tetrafluoroborate (CAS# 14283-07-9) 0-5%
n-Methyl Pyrrolidinone (CAS# 872-50-4) 0-1%
Oxalic Acid (CAS# 144-62-7) 0-1%
Propylene Carbonate (CAS# 108-32-7) 0-15%

One of our erstwhile cpf'ers showed me a link to some testing that was done with Li-Ion cells:
http://www.pcpitstop.com/pcsafety/video.asp

[IsaacHayes]

Hmm. Just read through the .pdfs.

If one were to drop one, or it leaked, but not vent with flame/etc, the chemicals can still get fluoride into your skin and make you sick right?

[David_Campen]

If one were to drop one, or it leaked, but not vent with flame/etc, the chemicals can still get fluoride into your skin and make you sick right?

Make you sick? That is a subjective question. Do you worry about getting sick from the fluoride that is put in your toothpaste?