Video 1: Assembling the PAT-Cell:
The test procedure is to cycle the graphite electrode with a constant current of 1 mA between V1R = 2.5 and 0.005 V. Intermittently, every 5 minutes, a small sinusoidal current is superimposed on the direct current at frequencies between 10 kHz and 1 Hz to measure the impedance.
Video 2: EL-Software – Writing the test procedure
Video 3: EL-Software – Running the experiment
The diagrams in figure 2 show from bottom to top the applied current i12, the voltages (V12, V1R, V2R) and the impedances (magnitudes of Z12, Z1, Z2 at 1 Hz) of the full cell and the individual electrodes.
What do we observe ?
Notably, the cycle of the anode half-cell has to start with negative current (discharge) so as to mimic what happens at the graphite electrode in the “full” Li-ion battery (NCM vs. Graphite) during first charge. Consequently, at the beginning of the cycle, the lithium metal electrode (2) is getting dissolved, and lithium ions are getting inserted into the graphite electrode (1). The dissolution of lithium metal leaves behind a smooth (i.e. low surface area) electrode covered with the SEI layer and consequently the impedance Z2 of the lithium electrode remains high throughout the initial half cycle. This situation changes with the reversal of the current direction after 6.2 hours. Now lithium ions are extracted from the graphite lattice and deposited as a porous layer of dendritic metal on the lithium metal electrode. This increase in surface area leads to the observed decrease of |Z2| in the second half cycle.
The Coulomb efficiency for the graphite lithiation is 93% in the first cycle and >99% in the consecutive cycles (see Figure 3). In contrast, the Coulomb efficiency for the deposition/dissolution of lithium never exceeds 95% (taking that number from our previous application note for the plating on stainless steel). The porous and thus low-impedance lithium metal deposited during a given half cycle has thus been fully consumed in the next half cycle when the graphite electrode is still about 5% away from full lithiation. This last 5% must be dug out of the original non-porous (and therefore high-impedance) lithium metal foil, resulting in the observed rise in the impedance Z2. This behavior is seen for the first time after 18 hours and then during each consecutive cycle. We saw and discussed the same effect in the last application note for the NCM half cell.
Again, the lithium metal is lost by electrical disconnection of metallic lithium (Li0) pockets during dendrite growth and dissolution. The disconnected but still metallic lithium can be observed as a greyish residue in the separator and on the surface of the lithium metal electrode when dismantling the PAT-Cell after the cycle experiment.
Video 4: Disassembling the PAT-Cell
What can we conclude?
- Graphite against lithium metal is not only a poor battery in that it stores almost no energy, but, more surprisingly, it is also a poor experimental model for the graphite anode in the lithium-ion battery.
- Almost all the time during the cycle experiment, the metal electrode rather than the graphite electrode is the bottleneck for charge transport. Especially in the initial cycle and then always at the end of graphite lithiation, when the cell voltage is close to zero, the high overvoltage at the lithium metal electrode leads to a premature termination of the cycle and thus to an incorrect (too small) capacity. Due to the flat voltage profile, this is much more problematic with the graphite half cell than with the NCM half cell.
- Just as with the NCM half cell, lithium dendrites can prematurely end the life of the cell. The porous layer of dead lithium will consume electrolyte, causing the cell to dry out and lose capacity. And also the soluble reaction products of the intensive SEI formation on the lithium metal can unpredictably influence the performance of the cell
Build your test cells with the anodes and cathodes that are actually in the finished battery. Only use a lithium metal anode if you want it to be in the finished battery. And whether you work with or without a lithium metal anode, always use a reference electrode as a third electrode. Whenever possible. Did I mention that already in the previous app note?
Next time we will finally deal with the real lithium ion battery made of NCM and graphite. Completely without lithium metal, except of course for the reference electrode.
Stay tuned (and healthy).
— by Dr. Matthias Hahn, Dr. Annika Baumann, Margaryta Paramonova, Daniel Wilke