Federal Register :: Hazardous Materials; Transportation of Lithium Batteries

This may result in a thermal runaway caused by the exothermal reactions in the battery6,7,8,9,10, eventually resulting in a fire and/or explosion. The consequences of such an event in a large Li-ion battery pack can be severe due to the risk for failure propagation11,12,13. The electrolyte in a lithium-ion battery is flammable and generally contains lithium hexafluorophosphate (LiPF6) or other Li-salts containing fluorine. In the event of overheating the electrolyte will evaporate and eventually be vented out from the battery cells.

FedEx states marking a package “PRIMARY LITHIUM BATTERIES—FORBIDDEN FOR TRANSPORT ABOARD PASSENGER AIRCRAFT” will only cause confusion, delay shipments and impede commerce.
However, the ventilation flow is large and the O2 released from the battery cells is regarded as negligible.
Figure 6 shows the repeatability results for four tests of battery type B for 100% SOC.
At its 2006 meeting (October 25—November 3, 2006), the ICAO Dangerous Goods Panel further considered amendments to the ICAO Technical Instructions concerning lithium battery safety.
FEDCO states the majority of its sales are to distributors and dealers of computer products and to battery retail stores, with major competition from foreign importers of primary lithium batteries.

A cell or battery and equipment containing a cell or battery that was first transported prior to January 1, 2006 and is of a type proven to meet the criteria of Class 9 by testing in accordance with the tests in the UN Manual of Tests and Criteria, Third Revised Edition, 1999, need not be retested. Retain the current exception for medium-size lithium batteries and cells shipped in or with equipment from the Class 9 shipping requirements for all modes. The FAA tests demonstrated that the lithium output from a single burning primary lithium battery is sufficient to penetrate single-layer cargo linings.

Batteries

Other commenters also question the validity of the tests cited in the IFR and our use of the test results as a basis for prohibiting the air transportation of primary lithium batteries and cells. For example, NEMA questions whether PHMSA has improperly relied on the FAA test report, which addresses a worst-case scenario for bulk shipments of lithium batteries, in limiting the transportation of single batteries or products packed with or contained in equipment. NEMA states that unlike “bulk shipments” of primary lithium batteries, batteries packed with or contained in equipment are not close in proximity to each other during transportation.

The protective boxes and steel net were fastened in the wire gratings with steel wire and steel straps to avoid movement due to response to the fire.
Although we insist that regulatory actions be data-driven, we will not wait for accidents to address known risks.
Fisher Scientific suggests an exception for small primary lithium batteries would provide an adequate level of safety with a minimum of operational disruption and no negative economic impacts.
In the alternative, Intel states any further restrictions on shipments of primary lithium batteries on passenger aircraft should include rational thresholds based on the weight of the batteries, not the weight of packages.
Based on its longstanding experience shipping products containing small primary lithium batteries, Intel contends no further restrictions on shipments of primary lithium batteries is warranted.

The study included large-sized automotive-classed cells, i.e. series production cells of high industry quality, with long life time etc. This requirement does not apply to lithium cells or batteries packed with equipment. PRBA and other commenters suggest PHMSA separate the provisions in the HMR governing the transportation of primary lithium cells and batteries from those governing secondary lithium cells and batteries. To alleviate any confusion, PRBA suggests PHMSA incorporate into the HMR a new section specific to secondary lithium cells and batteries. Figure5 shows the results for type B cells with and without exposure to water mist, note that both the HRR and HF production are delayed when water mist is used. In this limited study, the peak of the HF production rate increased by 35% when using water, however no significant change in the total amounts of the HF release could be seen.

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Further, primary lithium batteries are capable, on their own, of initiating a fire that could have catastrophic consequences. The FAA report on the flammability characteristics of primary lithium batteries raises significant concerns justifying our conclusion that they should be prohibited aboard passenger carrying aircraft. URS Corporation suggests PHMSA remove the marking requirement “PRIMARY LITHIUM BATTERIES—FORBIDDEN FOR TRANSPORT ABOARD PASSENGER AIRCRAFT” for packages transported by highway, rail, and vessel with no air transportation involved. The commenter states that, because much, if not all, cargo within ULDs is no longer visible, the only means to identify prohibited primary lithium batteries is not available. However, the comments raise legitimate concerns about the costs that may be incurred by companies, particularly small businesses, if we were to remove the exception in its entirety.

For other SOC values the fluoride content is higher from the gas-washing bottle measurements.
The reason for this experiment is that water is the preferred extinguishing agent for a lithium-ion battery fire.
These commenters suggest the incident occurred under atypical handling procedures and was the direct result of inadequate packaging.
(1) The lithium content of each cell, when fully charged, is not more than 5 grams.
The total amount of HF varies considerably for the different battery types, see Fig.
FedEx recommends the use of Cargo Aircraft Only labels for the shipment of lithium batteries subject to the final rule.

Still the battery test setup allowed that the separators and electrical insulation in the cells could melt due to the heat exposure which could cause various internal and external electrical contacts. This is the first paper to report measurements of POF3, 15–22 mg/Wh, from commercial Li-ion battery cells undergoing abuse. However, we could only detect POF3 for one of the battery types and only at 0% SOC, showing the complexity of the parameters influencing the gas emission. Repeated tests were performed for battery types A-C for selected SOC-levels. Some of the repetitions included a variant, e.g. including water mist; see Methods.

Lithium-ion battery fire tests

FedEx states that there appears to have been more problems with non-bulk shipments of primary lithium batteries as opposed to bulk shipments and that the FAA flammability test was conducted only on bulk shipments of primary lithium batteries. FedEx recommends that the FAA examine non-bulk shipments of primary lithium batteries and conduct appropriate tests on these types of primary lithium battery shipments. The Air Transport Association of America (ATA) supports the proposals in the April 2002 NPRM, but notes a number of its members are particularly concerned about the retention of the exception for small lithium batteries as proposed in the NPRM. ATA states such provisions will be confusing to transport workers involved in accepting, sorting and loading packages in air transportation. According to ATA, air carriers are concerned that an indication on a package that it contains “lithium batteries” may cause packages to be removed from the system for clarification or possible rejection. The removal of a package from the system could occur more than once during the transportation cycle.

Toxic fluoride gas emissions from lithium-ion battery fires

Other types of gas emissions from Li-ion cells during abuse have been the subject of a somewhat larger number of investigations33,34,35,36,37,38,39,40,41. Since the electrolyte typically is the primary source of fluorine, measurements of fluorine emissions from battery type electrolytes have been studied. For example, fire or external heating abuse tests have been performed on electrolytes42,43,44,45,46 and the quantitative amounts of HF and POF3 have been measured in some cases45,46. Other studies of electrolytes exposed to moderate temperatures, 50–85 °C, show the generation of various fluorine compounds20,21,47,48,49 and some studies include both electrolyte and electrode material50,51,52. Lithium-ion battery fires generate intense heat and considerable amounts of gas and smoke.

The sand bed for the propane burner is underneath the wire grating, a pilot flame (seen in front left corner of the burner) is used to ignite the propane gas. (5) Be equipped with an effective means of preventing external short circuits. A regulation identifier number (RIN) is assigned to each regulatory action listed in the Unified Agenda of Federal Regulations. The Regulatory Information Service Center publishes the Unified Agenda in April and October of each year. The RIN number contained in the heading of this document may be used to cross-reference this action with the Unified Agenda.

The selected SOC level in each test was set using a charge/discharge procedure using ordinary laboratory equipment as well as dedicated battery test equipment, i.e. a Digatron battery tester and Metrohm Autolab PGSTAT302N with 20 A booster module. The cells were first fully charged by constant current followed by constant voltage (CC-CV) according to the manufacturer’s instructions. For cells intended for tests with less than 100% SOC, the cell was discharged to the selected SOC level, using constant discharge current (CC). A relative low current rate, about C/5, was used Nebido 1000 mg and voltage and current rates were within the manufacturer limits. However, the tests for type C and D were split in several test periods, for type C repetitions on 50% SOC were conducted in all three test periods, and for type B repetitions at 100% SOC were made in two test periods, the latter one included a water mist test. Repeatability for four tests of type B cells at 100% SOC, (a) shows the heat release rate (burner HRR contribution is subtracted) and (b) shows the HF release, both as the measured concentrations as well as the calculated HF production rates.

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

Some HF might not have been collected in the measurements and the effect of this error is largest for the batteries that give the lowest values. The battery surface temperature was measured with several type K thermocouples; the number of sensors varied for the different battery types. Battery cell surface temperature values presented in this paper are average values over the cell. Cell voltage and thermocouple readings was sampled with 1 Hz using two types of data loggers, Agilent A using an Agilent A reed multiplexer module (for the third test period) and Pico Technology ADC-24 (for the first and second test period). The toxicity of HF and the derivate hydrofluoric acid is well known22,23,24 while there is no toxicity data available for POF3, which is a reactive intermediate25 that will either react with other organic materials or with water finally generating HF.