Inhaled vapors from battery!!!

[LED61]

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]

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]

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]

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]

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

 

[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?

 

[IsaacHayes]

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

 

[David_Campen]

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.

 

[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.

 

[NewBie]

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.

 

[David_Campen]

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.

 

[choppers]

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

 

[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.

 

[MorePower]

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.

 

[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.

 

[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