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September 15, 2016

THE REAL SCIENCE BEHIND BATTERY SAFETY

Chemistry
Manufacturers
Safety
Nadim Maluf

A recent article published by The Verge attempted to explain the science behind the exploding Samsung Note 7 batteries. The article touches on several important aspects of battery safety but the handwaving did not really talk about much science. So this post will address a failure mode of lithium-ion batteries and how defects can form during manufacturing with catastrophic results.

One of my earlier posts described the inner structure of a lithium battery. In a nutshell, there are alternating material layers that form the basic structure of the battery: a sandwich of two electrodes, called the anode and the cathode, with an insulating separator between them. During manufacturing, these layers are assembled then rolled together like a cigar before they are packaged into a protective sleeve. This is a gross simplification but highlights the basic structure and assembly of the lithium-ion battery. With some minor exceptions, the manufacturing is primarily an assembly process, and does not resemble in any form the manufacturing processes used in semiconductor devices.

The first figure below shows a rudimentary drawing of the basic structure of the lithium-ion cell. The graphite anode, shown in black, sits counter to the cathode, shown in green. The separator, shown in blue, is sandwiched between the two electrodes and acts as an insulator, in other words, its primary function is to prevent internal electric shorts between the two conductive electrodes. We all know that electric shorts are not good!

One of the basic requirements in the design of the battery is for the graphite anode to physically extend beyond the edges of the cathode. In other words, the anode is wider than the cathode at every point, especially the long edges of the sheets. This is needed to maintain safety within the cell and prevent the formation of lithium metal. Intuitively, there has to be more anode material than cathode material to absorb all the lithium ions. When the anode is not properly sized, the excess lithium ions will deposit as lithium metal, and that is called lithium plating. If you would like to dig a little deeper into lithium plating, this earlier post will shed some additional insight.

In practical terms, the anode is wider than the cathode ever so slightly, only a few percents. Any extra width of the anode does not participate in energy storage. In other words, the extra width of the anode is required for safety reasons, but does not contribute to charge storage. So battery designers go to extremes to optimize the extra width of the anode for the requisite safety.

As energy density increases, these battery designers have limited choices, one of them is to reduce the width margin of the anode. This means that the additional width of the anode relative to the cathode is now at its bare minimum. Any errors in manufacturing that jeopardize this extra overlap may have dire consequences.

So now let’s examine one particular manufacturing defect where a slight misalignment between the anode and cathode occurs during the assembly process. The figure below shows the same structure as above but now the anode layer is shifted ever so slightly to the right.

At the misaligned edge, the requisite overlap of the anode relative to the cathode is now diminished or even possibly vanished. The A/C ratio at this locale drops below the requisite limit for ensuring safety. The result, as you expected, is the onset of lithium metal at this edge. The lithium metal forms on the anode edge. As the lithium metal grows in size and thickness, it ultimately punctures the separator and causes an electrical short between the anode and cathode. Boom! we now have a catastrophic failure.

So this begs the question: why did Samsung release new software that limits the maximum charge in the faulty Galaxy Note 7 to only 60% of maximum? It is because the risk of lithium metal plating heavily depends on the voltage and the maximum charge in the battery. This is evident in the voltage chart of this earlier post: the higher the voltage, i.e., the higher maximum allowed charge, the higher the risk of lithium metal plating.

I will close by reiterating one final thought. The tolerance requirements in the manufacturing of lithium ion batteries have risen sharply with increasing energy density. Short of using new materials (that still do not exist in commercial deployment), increasing the energy density means reducing all the extra space inside the battery that is not made of anode and cathode materials. These are the only two materials that store energy. Everything else is just overhead…i.e., dead weight. They are still needed for other functions and safety, but they do not contribute to storing electrical charge. So battery designers keep reducing this overhead and in the process, make the manufacturing tolerances every so tight….and that is a recipe for many disasters to come unless we start adding a lot more intelligence to the battery to avoid and mitigate these undesired situations.

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