# 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/ESMSDSs/MSHydFluoricAcid.html#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.


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## SilverFox

Hello LED,

Glad to hear you are OK.

Tom


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## 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... :thinking:


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## 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.


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## 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.


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## 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?

:candle:


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## RA40

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


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## 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!


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## 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...


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## MrAl

Hi there,

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


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## 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.


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## 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?


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## Size15's

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

Al


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## 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.


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## Handlobraesing

LED61 said:


> 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.


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## KROMATICS

prof said:


> 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.


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## LED61

Handlobraesing said:


> 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


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## 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.


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## 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...


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## Sigman

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


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## LED61

David_Campen said:


> 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.


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## Art Vandelay

David_Campen said:


> 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


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## 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?


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## David_Campen

daveman said:


> 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.


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## 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?


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## David_Campen

LED61 said:


> 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.


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## greenLED

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


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## NewBie

IsaacHayes said:


> 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/globalcitizenship/environment/pdf/msds_lg_liion.pdf

Molicel:
http://www.tek.com/Measurement/cgi-...ment/Service/msds/index.html&FrameSet=service

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

International Battery Li-Ion:
http://www.internationalbatteryinc.com/MSDS/MSDS_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


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## 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?


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## 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?


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## IsaacHayes

The fluoride in toothpaste is likely less concentrated than the stuff inside the electrolyte of the cell...


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## David_Campen

IsaacHayes said:


> The fluoride in toothpaste is likely less concentrated than the stuff inside the electrolyte of the cell...


Toothpaste contains fluoride equivalent to about 0.2% sodium fluoride. From the Duracell MSDS a 123 cell contains a maximum of 5% trifuoromethanesulfonate. So, it would probably be a good idea to not use the insides of a 123 cell as toothpaste.


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## NewBie

Breaking out the Energizer Li-Ion chemicals:

Energizer Lithium Ion:

Acetylene Black (CAS# 1333-86-4) 0-2%
http://www.itcilo.it/english/actrav/telearn/osh/ic/1333864.htm

Biphenyl (CAS# 92-52-4) 0-15%
Synonyms: Diphenol; 1,1'biphenyl; phenylbenzene 
3. Hazards Identification
Emergency Overview 
-------------------------- 
WARNING! HARMFUL IF SWALLOWED, INHALED OR ABSORBED THROUGH SKIN. CAUSES IRRITATION TO SKIN, EYES AND RESPIRATORY TRACT. MAY AFFECT LIVER, CENTRAL AND PERIPHERAL NERVOUS SYSTEMS. MAY CAUSE ALLERGIC SKIN REACTION. 

Potential Health Effects 
---------------------------------- 

Inhalation: 
Inhalation of dust or vapors can irritate the mucous membranes and respiratory tract. Other symptoms may parallel those from ingestion exposure. 
Ingestion: 
Exerts toxic effects on the central nervous system and liver. Symptoms may include headache, diffuse gastro-intestinal pain, nausea, numbness, body aches, and general fatigue. 
Skin Contact: 
May cause irritation. May be absorbed through the skin with symptoms paralleling those from ingestion exposure. May cause allergic reaction in sensitive individuals. 
Eye Contact: 
Vapors and dust cause eye irritation. 
Chronic Exposure: 
Chronic exposure may cause peripheral nerve damage and liver injury. 
Aggravation of Pre-existing Conditions: 
No information found. 
http://www.jtbaker.com/msds/englishhtml/b2347.htm

Diethyl Carbonate (CAS# 105-58-8) 0-15%
EXPOSURE 
PREVENT GENERATION OF MISTS! 
•INHALATION Cough. Nausea. Sore throat. 
•SKIN 
Protective gloves. 
Rinse and then wash skin with water and soap. 
•EYES Redness. Pain. 
http://www.cdc.gov/niosh/ipcsneng/neng1022.html
See effects on animal testing, tumors and reproductive
http://www.cdc.gov/niosh/rtecs/ff958940.html


Dimethyl Carbonate (CAS# 616-38-6) 0-15%
•INHALATION Cough. 
•SKIN Protective gloves. 
•EYES Redness. 
http://www.cdc.gov/niosh/ipcsneng/neng1080.html
ACUTE TOXICITY DATA AND REFERENCES: see 50% mouse kill levels
http://www.cdc.gov/niosh/rtecs/fg6ddd0.html


Ethyl Methyl Carbonate (CAS# 623-53-0) 0-15%
Ethylene Carbonate (CAS# 96-49-1) 0-15%
Information pertaining to particular dangers for man and environment
R36 Irritating to eyes
Primary irritant effect:
-on the skin: Irritant to skin and mucous membranes.
-on the eye: Irritating effect
Ethylene Carbonate is irritating to the skin, eyes, mucous membranes and upper respiratory tract.
http://www.alfa.com/MSDSPDF/English/A15735.pdf

Graphite (CAS# 7782-42-5) 7-22%

Lithium Cobalt Oxide (CAS# 12190-79-3) 15-30%
Information pertaining to particular dangers for man and environment
R 40 Limited evidence of a carcinogenic effect.
R 43 May cause sensitization by skin contact.
Substance is listed in Toxic Substance Control Act (TSCA) inventory.
Acute toxicity:
Primary irritant effect:
on the skin: Irritant to skin and mucous membranes.
on the eye: Irritating effect.
Sensitization: Sensitization possible through skin contact.
Subacute to chronic toxicity:
Cobalt is an experimental neoplastigen and tumorigen. It is an experimental carcinogen of the connective tissue and lungs. Cobalt metal and inorganic compounds are classified as an animal carcinogen by the ACGIH. Ingestion may cause burning in the mouth, esophagus, and stomach. Inhalation of dusts and fumes may cause irritation of the respiratory tract and labored breathing and coughing. Sensitization, nausea,
flushing of the face and ringing in the ears is also possible.
http://www.alfa.com/MSDSPDF/English/14049.pdf

Lithium Hexafluorophosphate (CAS# 21324-40-3) 0-5%
3. HAZARDS IDENTIFICATION
Designation HARMFUL ~ IRRITANT
Risk Phrases R20/21/22 H a rmful by inhalation, in contact with skin and if
R36/37/38 Irritating to eyes, respiratory system and skin.
Hazardous Products of Combustion may include : hydrogen fluoride (hydrofluoric acid), phosphorus pentoxide, phosphoric acid.
6. ACCIDENTAL RELEASE MEASURES
Personal Protection Avoid inhalation or contact of spilled material with skin or clothing. Wear protective equipment including rubber gloves, and eye protection. Keep unprotected persons away.
http://www.alfa.com/MSDSPDF/English/B20964.pdf
11. Toxicological information:
Fluorides may cause salivation, nausea, vomiting, diarrhea and abdominal pain, followed by weakness, tremors, shallow respiration, convulsions and coma. May cause brain and kidney damage. Chronic fluoride poisoning can cause severe bone changes, loss of weight, anorexia, anemia and dental defects.
Inorganic phosphorus compounds may cause irritation and hemorrhages in the stomach as well as liver and kidney damage. Bone structure may be attacked, especially the jaw and teeth.
http://www.alfa.com/MSDSPDF/English/11529.pdf

Lithium Tetrafluoroborate (CAS# 14283-07-9) 0-5%
3. HAZARDS IDENTIFICATION
Designation HARMFUL ~ IRRITANT
Risk Phrases R20/21/22 H a rmful by inhalation, in contact with skin and if swallowed.
R36/37/38 Irritating to eyes, respiratory system and skin.
10. STABILITY AND REACTIVITY
Specific Hazard
Incompatibilities Strong oxidising agents. Strong acids.
Decomposition Hazardous products of decomposition may include : hydrogen fluoride (hydrofluoric acid).
http://www.alfa.com/MSDSPDF/English/A10607.pdf
Eye Contact: Immediately flush eyes with plenty of water for at least 20 minutes. Assure adequate flushing of the eyes by separating the eyelids with fingers. Get immediate medical attention if irritation persists, or symptoms of overexposure become apparent.
Skin Contact: Immediately wash skin with plenty of water for at least 20 minutes, while removing contaminated clothing and shoes. Get medical attention especially, if irritation develops, persists, or symptoms of overexposure become apparent.
http://www.alfa.com/MSDSPDF/English/L16800.pdf

n-Methyl Pyrrolidinone (CAS# 872-50-4) 0-1%
EXPOSURE 
PREVENT GENERATION OF MISTS! 
•INHALATION Headache. 
•SKIN MAY BE ABSORBED! Dry skin. Redness. 
•EYES Redness. Pain. Blurred vision. 
CHEMICAL DANGERS:
The substance decomposes on heating or on burning producing toxic fumes including nitrogen oxides, carbon monoxide 
EFFECTS OF SHORT-TERM EXPOSURE:
The substance irritates the eyes and the skin. If this liquid is swallowed, aspiration into the lungs may result in chemical pneumonitis. 
http://www.cdc.gov/niosh/ipcsneng/neng0513.html
MUTATION DATA AND REFERENCES: 
sex chromosome loss and nondisjunction 
REPRODUCTIVE EFFECTS DATA AND REFERENCES: Numerous present, see link below:
http://www.cdc.gov/niosh/rtecs/uy585930.html

Oxalic Acid (CAS# 144-62-7) 0-1%
FIRE Combustible. Gives off irritating or toxic fumes (or gases) in a fire. 
EXPOSURE 
AVOID ALL CONTACT! 
IN ALL CASES CONSULT A DOCTOR! 
•INHALATION Sore throat. Cough. Burning sensation. Shortness of breath. Laboured breathing. Symptoms may be delayed (see Notes). 
•SKIN Redness. Skin burns. Pain. Blisters. First rinse with plenty of water, then remove contaminated clothes and rinse again. Refer for medical attention. 
•EYES Redness. Pain. Loss of vision. Severe deep burns. 
•INGESTION Sore throat. Burning sensation. Abdominal pain. Vomiting. Drowsiness. Shock or collapse. Convulsions. 
CHEMICAL DANGERS:
On contact with hot surfaces or flames this substance decomposes forming formic acid and carbon monoxide. The solution in water is a medium strong acid. Reacts violently with strong oxidants causing fire and explosion hazard. 
EFFECTS OF SHORT-TERM EXPOSURE:
Corrosive. The substance is corrosive to the eyes, the skin and the respiratory tract. Corrosive on ingestion. Inhalation of aerosol may cause lung oedema (see Notes). The substance may cause effects on the kidneys. Exposure far above the OEL may result in death. Medical observation is indicated. 
The symptoms of lung oedema often do not become manifest until a few hours have passed and they are aggravated by physical effort. Rest and medical observation are therefore essential. Immediate administration of an appropriate spray, by a doctor or a person authorized by him/her, should be considered. Do NOT use in the vicinity of a fire or a hot surface
http://www.cdc.gov/niosh/ipcsneng/neng0529.html
Additional effects:
http://www.cdc.gov/niosh/rtecs/ro256250.html

Propylene Carbonate (CAS# 108-32-7) 0-15%
Primary irritant effect:
on the skin: irritant to skin and mucous membranes.
on the eye: irritating effect
Subacute to chronic toxicity:
Internal exposure to propylene carbonate may cause somnolence or altered sleep time.
http://www.alfa.com/MSDSPDF/English/L06006.pdf

This is just some links and is not at all inclusive, but just to show some of the items about the chemicals present in Li-Ion cells.


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## NewBie

David_Campen said:


> Toothpaste contains fluoride equivalent to about 0.2% sodium fluoride. From the Duracell MSDS a 123 cell contains a maximum of 5% trifuoromethanesulfonate. So, it would probably be a good idea to not use the insides of a 123 cell as toothpaste.



Take a gander above. Toothpaste is not exposed to combustion upon failure of a cell, producing HF gas which combines with moisture in air to form hydrofluoric acid.

The warnings are on the MSDS sheets, so read the links I posted above.


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## David_Campen

NewBie said:


> Take a gander above. Toothpaste is not exposed to combustion upon failure of a cell, producing HF gas which combines with moisture in air to for hydrofluoric acid.
> 
> The warnings are on the MSDS sheets, so read the links I posted above.


And neither is this thread, or the specific post that I was responding to, about a cell that was exposed to combustion.


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## choppers

sure am glad that you are ok, thank you for the information...


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## LED61

David Campen, I WILL NOT waste my time arguing with you about this. You do a great disservice to this community by insinuating battery vapors are safe to inhale, whether the battery burns or not. The vapors emmited from the battery I dropped were not present in the other 69 batteries I had next to it, they only smelled like flashahol, like you stated and that is ok so in answer to your statement I will continue to use lithium batteries. I handle display fireworks and shells I can handle batteries. 

For the record, I am not a chemist and whatever information I have posted here comes from the research I´ve done and the doctor´s opinion and based on what happened that´s it. Take it or leave it.

In regards to the HF, maybe the doctor is wrong and so are the other posters more knowledgeable on the matter. I don´t know if it is correct to assume Hydrofluoric acid was emmited by a battery that was not burning, it may not have been, but then there must have been something else so toxic so as to cause the initial delayed reaction of chest pain, shortness of breath, coughing, and weakness in the limbs.

Blah blah blah and I´m not going to do a full analysis of what exactly was that came out of that thing but it was not flashahol and it was toxic and my body did react to it 20 minutes later in a very ugly manner. This is the risk one takes by taking the time to write about something odd and hard to believe, and there will always be skeptics like you thinking the whole thing is made up or phsycological. I´m really glad I pulled out of this OK and it did really scare me I wont lie about it.

As far as LunarModule, I´ve read the whole thread and after what happened to me I would not dismiss one bit what happened to him. I know this member lacks credibility and has been questioned, and I don´t know him, but all he says is entirely possible to me.


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## MorePower

NewBie said:


> Take a gander above. Toothpaste is not exposed to combustion upon failure of a cell, producing HF gas which combines with moisture in air to form hydrofluoric acid.



Not to nitpick, but HF gas is hydrofluoric acid. Combining with water doesn't make it an acid.

I'd have more (what I consider) constructive things to add to this topic, but *David_Campen* has pretty much summed up my feelings and is getting a message board beatdown by people who seem to like spreading FUD. I'm pretty sure the effects *LED61* felt were real, as I've taken a good whiff of Li-MnO2 electrolyte by accident when the fume hoods in the dry room weren't on, but I'd wager that it was the electrolyte and not HF that caused it. The electrolyte can be pretty bad by itself.


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## LED61

MorePower, it could very well be you are correct. Since I have not submitted the battery for a thorough analysis it would be premature to assume HF was indeed released and I´d buy into the idea that what I smelled was a good whiff of Lithium Manganese dioxide like you put it. But it is sure toxic especially since it would be a concentrated solution that I smelled right off the vent holes.


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## JanCPF

LED61,
Thank God you're alright now.

I'm still unclear as to whether the nasty Hudrofloric acid can vent from Li-Ions as well, or whether this nasty stuff is something only associated with Lithium primaries. Sorry if this was actually answered, but I must have missed it then. 

BTW isn't Hydrofloric acid what people are using for difusing/etching the glass bulb on lamp assemblys to rid the beam of artifacts? Sounds like they are playing with dangerous stuff.

Jan


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## LED61

Hello Jan, Hydrofluoric acid is very dangerous, here is the MSDS for hydrofluoric acid

http://www.bu.edu/es/labsafety/ESMSDSs/MSHydFluoricAcid.html#anchor888417

As I´ve stated before, I am unsure whether this vented out of the cell or not. Seems it was not as apparently the cell has to undergo thermal degradation (heat, fire, explosion) for this to be vented out. But to answer your question about the acid there is the link.
Thanks

Alberto


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## js

LED61,

So very glad to hear that you are OK and feeling well at this point. Do you feel as if you've made a 100 percent recovery?

Do you still have the cell in question? I'd love to know how common a dangerous emission due to drop is, and what sort of emission is actually emanating from it, and how dangerous it is. I wonder if NewBie could extract that information from the cell if you mailed it to him?

For the record, I don't have any doubt whatsoever that you experienced something real. Having your wife drive you to the emergency room was prudent and wise. It seems to me that if you had completely forgotten about the incident and were watching a movie or TV, that it COULD NOT have been psychosomatic. Not entirely, anyway.

I'm sorry that you had to endure several insulting and offensively worded posts within this thread, but I'm glad you were able to just ignore them and move on. Also wise and prudent.


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## LED61

JS, I don´t have the cell in question anymore, too bad. The last thing I saw before throwing it away is the smell had gone away completely but there was a small quantity of clear liquid on top of the positive button. I don´t know what to think. i don´t trust these Chinese made cells anymore. Even the Sanyo´s.
Thanks for the well wishes by the way. I experienced minor discomforts already posted the day after but then everything went away. I was probably overagressive posting the Hydrofluoric acid thing being vented, as more research has led me to believe this can only happen if the cell undergoes thermal degradation, which was not the case. But it was sure toxic I am 100% sure of that.


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## SilverFox

Hello LED,

Keep in mind that it is unusual for a CR123 cell to vent. You indicated that the cell was dropped, and that could have done some damage. I am not a chemist, and can not comment on how HF acid is produced, but it is possible to have a small short inside the cell as a result of physical damage. This small short can generate some heat, and if it get hot enough, can lead to thermal run away. If it does not get hot enough, it just dies away.

In order to get a more accurate idea of what the clear fluid was, perhaps you should have also tasted it...   

Tom


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## IsaacHayes

I read the MSDS that was posted, and IIRC the electroylte can cause your heart to be stimulated..

I've got a question, which is a little off topic but still related to lithium stuff. When you have an unprotected lithium-ion rechargable, and you allow it to be discharged past it's safe point, is there any hazard of it blowing up/venting? Or will it just make it so it won't ever hold a charge again?


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## SilverFox

Hello Isaac,

When you discharge a Li-Ion cell to a low voltage (some say a low voltage is 2.5 OCV, some say 3.0 OCV, and other say 3.3 OCV, so take your choice), the composition of the electrolyte is altered. There is no problem during over discharging. The problem comes the next time you charge it back up. 

Capacity is reduced, internal resistance is increased ( which means there will be more heat generated during both charging and discharging), and the risk of small internal shorts is increased due to the changes in the electrolyte. If the small shorts lead to bigger shorts, you end up with thermal run away and rapid venting with flame.

The degree of damage done by an over discharge is directly proportional to the depth of discharge and the amount of time the cell stays in the discharged condition. 

Tom


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## Coop

First of all, good to see you're allright. Really once again proves that handling batteries should be done with caution.


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## IsaacHayes

Thanks Tom. I just ordered a DSD and 2 unprotected cells, (going in a single cell light) so I just need to double check. In a 2 cell light, over discharge could result in reverse charging one cell. But I won't have that setup.


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## lucio

do batteries have an odour?

I just received today my e2d,and when i moved it i could ear some kind of a "moving" inside.

i opened the tail and I smelt something(and i left it opened to avoid pressure in case they were really venting). shouldn't a battery have no odour?

i think i'm being paranoid now


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## Size15's

lucio said:


> do batteries have an odour?
> 
> I just received today my e2d,and when i moved it i could ear some kind of a "moving" inside.
> 
> i opened the tail and I smelt something(and i left it opened to avoid pressure in case they were really venting). shouldn't a battery have no odour?
> 
> i think i'm being paranoid now



Yes, the CR123A batteries have an odour, and if your E2d is a new one with SF123A batteries then any odour you smell can be considered a normal baseline.


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## lucio

Size15's said:


> Yes, the CR123A batteries have an odour, and if your E2d is a new one with SF123A batteries then any odour you smell can be considered a normal baseline.



thanks for the prompt reply!


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## David_Campen

> do batteries have an odour?


Yes, all Lithium cells have an odour that people here refer to as flashahol. It is from ether like solvents that are used in the electrolyte. You will notice it any time you sniff a battery compartment that has had lithium cells in it. It is nothing to worry about.


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## Martini

SilverFox said:


> I am not a chemist, and can not comment on how HF acid is produced, but it is possible to have a small short inside the cell as a result of physical damage.


That's exactly what I was thinking. An internal short from physical shock would not be unheard of. Hydrolysis facilitated by the invasion of moisture into the electrolyte (LiPF6) is one mechanism of HF production in a primary; high-temperature electrolyte degradation is the other. Note that pure HF is used in the manufacture of LiPF6; perhaps poor QC at the factory could result in traces of HF in the battery. I suppose we'll never know for sure what came out of that battery. There are many other chemicals inside a lithium primary that could've affected you as well. If indeed you caused a short, consider yourself lucky that the battery didn't decide to melt a hole in the floor and burn your house down. Then you would've had other things to worry about inhaling. 

LED61, I hope you have a speedy recovery. If I were you, I'd be drinking all the water I could stand; it'll help your liver and kidneys do their thing.


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## LED61

Thanks Martini, this event is over for me...I'm pretty sure. This thread was revived today by Lucio. Lucio, the flashahol is a normal and common smell it wont hurt you. What I smelled was something different...stronger and uglier. And stupidly from a very short distance from source.


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## EngrPaul

David_Campen said:


> Yes, all Lithium cells have an odour that people here refer to as flashahol. It is from ether like solvents that are used in the electrolyte. You will notice it any time you sniff a battery compartment that has had lithium cells in it. It is nothing to worry about.


 
Thanks for your post. I have been wondering about this!


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## questwww

I was soldering a battery CR2032, and it exploded.
More or less, the gas was inhaled. Is it dangerous?
no effect I felt till now (6 hours)
is it okay? any suggestion?


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## DM51

Post #1 of this thread gives a good illustration of the potential problem. HF gas is very dangerous if inhaled. My advice to you would be to see a doctor.


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## LED61

I've done some digging since that incident a while back, and seems the electrolyte that leaked out was particularly toxic to me, but may not be to other people, depending on the level of threshold. In my case it was definitely not pleasant, at least as a temporary and somewhat delayed reaction (20 minutes). But the substance apparently was not hydrofluoric acid.
In questwww's case though, the battery exploded, and some of that (HF acid odor)may have come out. I'd follow DM51's advice and see a doctor. I belive some liver lab tests would confirm if it is fighting off toxicity.


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## hopkins




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