Toxic fluoride gas emissions from lithium-ion battery fires Scientific Reports

Those who wish to voluntarily apply the “Cargo Aircraft Only” label on excepted packages of primary lithium batteries are encouraged to coordinate with all parties in their transportation chain. In its comments, PRBA refers to the NPRM published on May 6, 2004 by PHMSA under Docket HM–224B (69 FR 25469), which proposed a requirement for https://chromoepiloges.gr/new-study-reveals-optimal-oxandrolone-dosage-for/ oxygen cylinders to be overpacked in a packaging that would allow the cylinder to withstand a temperature of 400° F for 3 hours. (On January 31, 2007 PHMSA published the HM–224B Final Rule (72 FR 4442).) PRBA questioned why the lithium batteries were subjected to higher temperature tests than the 400° F proposed for oxygen cylinders.

For the four tests of type B at 100% SOC the mean value of the total FTIR detected HF release is 166.8 mg/Wh with a standard deviation of 11.5 mg/Wh, as seen in Table3. 6b, shows that for 100% SOC the HF release is faster and reaches a higher value. 6b shows lower HF release peak values, however, the total HF release value from the FTIR measurement of 168 mg/Wh is close to the average value (166.8 mg/Wh, as seen in Table 3). In order to study the effects of water on gas emissions, fire tests have also been performed where a water mist was applied during the fire. The reason for this experiment is that water is the preferred extinguishing agent for a lithium-ion battery fire.

Rule

The small business impact analysis conducted for Docket HM–224E was included in the regulatory evaluation prepared for the Final Rule and is summarized below. A complete copy of the report is in the public docket for this rulemaking. All comments submitted to the Dockets Management System, under Docket Number PHMSA–04–19886 (HM–224E) and comments received at the public meeting have been considered in developing this final rule. Several commenters submitted comments that were outside the scope of this rulemaking. On June 15, 2005, we published an Initial Regulatory Flexibility Analysis (IRFA) (70 FR 34729) and requested comments on the potential small business impacts of the proposals in our April 2, 2002 NPRM.

• Therefore extending the prohibition to cargo operations is beyond the scope of this rulemaking.
• Intel Corporation (Intel) recommends PHMSA either rescind or significantly modify the IFR to make it inapplicable to shipments of small primary lithium batteries and cells contained in equipment.
• Note that the reported concentration values in ppm are only valid for the measurements in the smoke duct of our specific test equipment and method.
• Battery cell surface temperature values presented in this paper are average values over the cell.
• FEDCO expresses concern that most foreign importers of primary lithium batteries are “under the radar” in so far as PHMSA is concerned.

The calculated average HF ppm noise level was treated as an offset that had both negative and positive values, ranging from extreme values of about −2 to 3.5 ppm. This offset was compensated for by assuming a constant offset value and adding positive or negative offset values to the total HF release value. Note that the reported concentration values in ppm are only valid for the measurements in the smoke duct of our specific test equipment and method. The HF and POF3 concentration values (in ppm) were used for calculating the corresponding production rates (in mg/s) using the ideal gas law and taking into account the measured ventilation flow rate in the smoke duct. The propane burner was started 2 minutes into each test, as indicated with arrows in the result figures in the paper. The burner was active as long as there was a heat contribution from the burning batteries; therefore, the burner was active for different durations of time for different batteries and SOC-levels.

Lagrangian plume rise and dispersion modelling of the large-scale lithium-ion battery fire in Morris, USA, 2021

The wire grating was made of steel wire about 2 mm thick over a surface of about 300 × 300 mm. The cells were not electrically connected to each other (except the laptop packs of type G, see note in Table1). Type A-F was pure battery cells while type G was a complete laptop battery pack which included plastics box, electronics and cables. The chemical content of the polymer materials in the auxiliary components of the battery pack of battery type G is not known. It is possible, however not likely, that fluorine was included in some of the components, which in that case could have resulted in the production of HF.

• A more robust cargo compartment would be incompatible with the need for a depressurized environment.
• POF3, on the other hand, was found only in one of the cell types and only at 0% SOC.
• A summary of the significant issues raised by the public comments in response to the IRFA, a summary of the assessment of the agency issues, and a statement of any changes made in the proposed rule as a result of such comments.
• A part of the smoke duct flow was sampled to a Servomex 4100 Gas purity analyser where the oxygen content was measured by a paramagnetic analyser and CO and CO2 were measured by a non-dispersive infrared sensor (NDIR).

The rule adopted in this proceeding strengthens the current regulatory framework by imposing stricter and more effective safeguards, including design testing, packaging, and hazard communication measures, for certain types and sizes of lithium batteries in certain transportation contexts. Lithium batteries are considered a hazardous material for purposes of transportation regulation because they can overheat and ignite in certain conditions and, once ignited, can be especially difficult to extinguish. In general, the risks posed by lithium batteries are a function of battery size (the amount of lithium content and corresponding energy density) and the likelihood of short-circuiting or rupture. By comparison to standard alkaline batteries, most lithium-ion batteries manufactured today contain a flammable electrolyte and have a very high energy density. A lithium battery is susceptible to thermal runaway, a chain reaction leading to self-heating and release of its stored energy.

A. Overview of Lithium Battery Risks

SION Power asserts eliminating the exception for medium-size lithium batteries will adversely affect its commercial development and suggests that, in the case of primary lithium batteries, eliminating the exception will limit the size of batteries using smaller cells. SkyBitz favors scaling back the exception for medium-size lithium batteries by limiting the number of cells or batteries per package, rather than eliminating the exception. ACR Electronics, Inc. states PHMSA should retain the exception for medium-size lithium batteries provided they are contained in strong, waterproof safety equipment. To evaluate the hazards posed by primary lithium batteries in air transportation, FAA’s Technical Center initiated a series of tests to assess their flammability characteristics. FAA published a technical report detailing the results of the tests in June 2004 (DOT/FAAIARI–04/26).

E. Regulatory Flexibility Act, Executive Order 13272, and DOT Procedures and Policies

The NTSB suggests the proposed rule could be improved by requiring a package containing 12 small lithium batteries or 24 lithium cells to be classed as a Class 9 material, and subject to the labeling and shipping paper requirements of the HMR. The Airline Pilots Association International (ALPA) states it agrees new testing requirements are needed. For those reasons, PHMSA and FAA continue to believe the prohibition on the transportation of primary lithium batteries on passenger aircraft is appropriate and well-founded. Although some commenters questioned the original justification for the IFR, intervening developments have buttressed the record, calling further attention to primary lithium battery risks and strengthening the case for final regulatory action.

Therefore, in this final rule we are eliminating the exception for medium-size lithium batteries and cells of all types transported by aircraft or vessel, but retaining a limited exception for ground transportation (i.e., motor vehicle and rail car). This action improves overall safety by reducing the risk of lithium battery-related incidents in the transport modes that are inherently most vulnerable to high consequence accidents, while minimizing the costs for businesses that ship lithium batteries by motor carrier or rail. The Teamsters state PHMSA failed to address the safety concerns of cargo-only aircraft transporting primary lithium batteries and cells.

E. Regulatory Actions To Address Transportation Risks Posed by Lithium Batteries of All Types

In case the emitted gas is not immediately ignited the risk for a gas explosion at a later stage may be imminent. Li-ion batteries release a various number of toxic substances14,15,16 as well as e.g. At elevated temperature the fluorine content of the electrolyte and, to some extent, other parts of the battery such as the polyvinylidene fluoride (PVdF) binder in the electrodes, may form gases such as hydrogen fluoride HF, phosphorus pentafluoride (PF5) and phosphoryl fluoride (POF3). Compounds containing fluorine can also be present as e.g. flame retardants in electrolyte and/or separator17, in additives and in the electrode materials, e.g. fluorophosphates18,19, adding additional sources of fluorine. We believe that overall cost of the rule for small businesses is substantially less than $2.50 per shipment.