The Impact of High Pulsed Loading on the Fatigue of Electrochemical Energy Storage Devices B. Shrestha, D. A. Wetz, and P.M.

Novak Department of Electrical Engineering, University of Texas at Arlington, Arlington, Texas 76019, USA UT Arlington is researching the impact high pulsed loading has on high power electrochemical energy storage devices. Fundamental effects on aging due to high pulsed loading are being investigated by studying the capacity fade and changes in the cells electrochemical impedance [1]. Experiments have been performed in which a 3Ah LiNixCoyAl1-x-yO2 cell is discharged at rates as high as 83C (250 A) in a 10 kHz pulsed fashion for 140s. A 1C recharge procedure is used between discharge cycles. The experimental results obtained when cycling at elevated rates are compared to results obtained from a second identical cell which is charged using a 1C constant current (CC) - constant voltage (CV) procedure and discharged at a constant 1C rate. This paper describes the experiments performed and shows the impact high pulsed loading has on the aging and capacity fade of a high power lithium-ion battery after fifty cycles have been performed. Introduction Over the past few decades, the field ability of portable electronic devices has increased tremendously, stemming from the vast improvements in lithium-ion battery technologies made by Goodenough, et.al. in the late 1970s and early 1980s, from which the wireless revolution was born [2]. Since that time, many different chemistries, electrode materials, and electrolytes has improved safety, energy density, and power density. Historically, lithium-ion cells have possessed high energy densities but modest power densities. Recently, electrochemical cell manufacturers have produced high power cells with equivalent series impedances (ESRs) less than 1 m. The reduced ESR has considerably increased the application space for which electrochemical energy storage devices can be used, including hybrid and all-electric vehicles [3,4,5], electric-grid energy storage [6,7], electromagnetic launchers [8,9], and high voltage pulsed power sources [10,11,12,13], among others. An increase in energy density directly correlates to an increase in operational time before recharging. The benefits gained from improving a cells power density vary considerably depending upon the load. In electric vehicle applications, the acceleration performance improves as well as regenerative braking efficiency. The installation of energy storage devices which have high power densities on the electric grid improves their ability to source inrush currents to induction motors, pulsed currents to high frequency power electronic converters, and high power DC loads. Other applications that benefit from power dense cells include radar, Marx generators, and directed energy weapon systems. Many studies have evaluated how different lithium-ion battery technologies perform when they are used to source currents continuously at or below their 1C rating. However,

little documented research exists on how the same cells perform when they are discharged at rates well in excess of their rated values (10s to 100s of C), in a pulsed manner at high pulsed frequencies (10s of kHz). Shrestha et al. [14] and Chen et al. [15] have shown that high power electrochemical cells can source currents at high rates, up to a few 1000C, in the form of short pulses lasting about a tenth of a second. In her efforts, Chen developed two different versions of a low impedance load on which to evaluate the pulsed characteristics of high power cells, shown in Figure 1. Though the load performed well, it was action limited to a single pulsed discharge; therefore making it impossible to fully discharge cells and characterize them at high rates. As will be shown later, the low impedance load developed at UTA has improved upon these limitations.

Figure 1. Two versions of low impedance test stand developed by Chen. Version one of the test stand is shown on left and version 2 is shown on right [15]. Though high rate pulsed discharge has been shown to be possible, how the cell ages remains a mystery when repeatedly discharged at high rates. Typically, capacity fade determines the age of a cell. Another measurement of cell age comes from the change in the cells frequency dependent impedance. Many chemical and physical changes occur inside the cell and can effect these measurements. As the cycle count increases, these changes should influence the EIS and capacity fade. Some of these possible changes include altering of an electrodes structure, electrolyte decomposition, phase transition, growth of the solid electrolyte interface (SEI) layer, and metal dissolution. While the reliability of this technique remains unclear, some have proposed that the age of a cell can be tracked by the change of a cells EIS profile. If possible and reliable, it would be very beneficial to the electrochemical community. Li et al. [16] has previously shown EIS measurements they made while cycling a lithium-ion battery 286 times. As seen in Figure 2, their data shows that the Nyquist plot shifts to the left and the lower impedance semi-circle grows considerably as cycling progresses. Though this data shows that EIS curve changes, determining how changes in the EIS correspond to internal cell changes remains unclear.

Figure 2. Impedance spectra of a fully discharged lithium-ion batteries with different cycle number at 1 C rate: (a) 0; (b) 40; (c) 286 cycles [16] In order to better understand how cells age at high discharge rates, experimental research in this area has been initiated. As a platform on which to conduct the research, an improved version of the low impedance experimental test stand has been constructed [14]. In the results presented here, a 3 Ah LiNi xCoyAl1-x-yO2 (LNCAO) cell has been pulsed discharged at 10 kHz, with a 50% duty cycle, at current rates as high as 83C (250 A). The switching frequency and current rate have utility in the fieldable applications mentioned above. A description of the test stand, the experimental procedure, and a summary of the 83C pulsed discharge results obtained through the completion of fiftyone cycles will be presented. Experimental Setup The improved test stand mentioned above extracts high currents from a low impedance cell in a fast, pulse-width modulated manner [14]. A computer aided design (CAD) model of the test stand is shown in Figure 3, a circuit model is shown in Figure 4, and a photograph of the constructed stand is shown in Figure 5.

Figure 3. Computer aided design (CAD) model of the experimental test stand.

Figure 4. Electrical circuit schematic of the experimental test stand.

Figure 5. Constructed photograph of the experimental test stand in the discharge configuration. While many high quality, commercially available, low impedance battery evaluation systems are available; their high cost can be problematic [17,18,19] and even when this is not a factor, the system limitations set by the manufacturer make it difficult or impossible for the user to make changes when needed. In order to vary the test conditions easily, the test stand was constructed for a wide variety of experiments. In its current configuration, the test stand is able to sink continuous currents as high as 5 kA and pulsed currents as high as 10 kA from electrochemical cells or modules with potentials as high as 100 V. The test stand has been previously documented and used for a variety of pulsed discharge experiments. The reader is refereed to [14, 20, 21] for further information. As seen in Figure 3, the cell under test is housed in a thick walled stainless steel chamber to ensure that any thermal runaway events are safely contained. The positive terminal of the cell is oriented downward and is connected directly to a 1.58 cm diameter rod, which is one four conductors that makes up the variable resistor/inductor. This component is essentially a two turn inductor whose length varies by adjusting the vertical location of two saddle clamp conductors over the conductor length of 0.1 m to 1.5 m providing a circuit inductance range of 0.1 H to 2.3 H and resistance of 10 to 10s of m depending upon the type of rod material. The output of the inductor is terminated into the aluminum plate located below the cell. From the lower aluminum plate, the

current is fed into a total of sixty, 100 V 200 A MOSFETS connected in parallel. The MOSFETs are grouped, and trigger-able in six sets of ten enabling the stand resistance to be further tuned if needed. Large copper bus bars conduct the current up to the aluminum bus plate above the cell. This aluminum plate has another safety feature which enables the user to open the circuit mechanically if needed. From the center aluminum disk, the current feeds through a custom made 41 current viewing resistor (CVR) and finally back to the negative terminal of the battery. MOSFETs are used because of their low turn on voltage which is needed when single, low voltage cells are tested. Each one has an on-state resistance of roughly 8 m, therefore when all sixty are conducting they act as a roughly 185 resistance. The bus bars and contact impedance add an additional 159 of impedance giving the stand a minimum impedance around 350 . In t he experiments being performed here, a 83C discharge rate (250 A) is desired from a single cell which as a nominal ESR of roughly 0.93 m. The stand therefore requires an additional resistance of 1 m to be added in series. This is achieved by using a single turn of the variable inductor and a stainless T304/304L rod material. The one drawback in the current design of the test stand is the inability to vary the load resistance coarsely during an experiment. During each experiment, the cell voltage, current, and temperature are recorded using a high speed National Instruments data acquisition system. A 0.076 mm K-type thermocouple measures temperature. Voltage and current data is sampled at rates as high as 250 ksamples per second and thermal data is recorded at 100 samples per second. Two identical 3 Ah LNCAO chemistry lithium-ion batteries have been tested experimentally in the work presented here. The first cell is the variable cell which has been repeatedly discharged from 4.1 V to just under 2.0V at peak rate of 83 C (250 A) in a pulsed fashion. The cell discharges each time at a pulsed frequency of 10 kHz with a 50% duty cycle for roughly 140 seconds. After each discharge, the cell is recharged using a 1C constant current (CC) constant voltage (CV) procedure. The 1C recharge minimizes any aging induced during the recharge portion of the experiment. Before and after each 1C recharge, an electrochemical impedance spectroscopy (EIS) procedure is performed on the cell using a frequency sweep of 20 kHz to 10 mHz and signal RMS amplitude of 10 mV. After every five elevated discharge procedures, the cells capacity is characterized by performing a 1C-CC discharge using a potentiostat. The second cell functions as the control cell which undergoes a 1C-CC/CV recharge and 1C-CC discharge. As in the case of the variable cell, EIS measurements are made after each cycle. A flow chart describing the elevated rate discharge and 1 C recharge experiments performed on the variable cell is shown on the left hand side of Figure 6. A flow chart describing the 1 C charge and discharge procedures performed on the control cell as well as the 1C characterization procedure performed on both cells is shown in the right side of Figure 6.

Figure 6. Flow charts describing the experimental procedures performed on the variable and control cells. Experimental Results At the time of this writing, fifty-one cycles have been performed on each of the two cells. Complete voltage and current waveforms recorded during the third elevated discharge experiment are shown in Figure 7. As seen in the figure, the cells voltage initiates at roughly 4.1V and the cell is discharged at a peak rate of 83 C. The average cell current is roughly 200 A correlating to an average 66C rate for the full 140 seconds.

Figure 7. Voltage and current discharge profiles measured during cycle three. Comparative data recorded during cycles three and fifty-one respectively is shown in Figure 8. Note that in figure 8 the current in cycle fifty-one is slightly higher. However, this is a result of the cell voltage starting out ~0.08V higher than in cycle three.

Figure 8. First 500 s of the voltage and current discharge profiles measured during cycle three and cycle fifty-one respectively Figure 9 displays the temperature profiles recorded during the third and fifty-first cycles. Two measurements are made during each experiment with one being near the terminals of the cell and the other being near the center of the cell. In the figure, the vertical line at 140s represents the time at which the discharge was completed. Despite that, it can be seen that the temperature of the cell keeps rising even though the pulsed discharge has ended. This is a result of the thermal diffusion time required to heat the cells containment. In both cycles, the temperature does not exceed 50 oC indicating that cell temperature should not be a major contributor to the cells aging during the experiments. It can be seen that the temperature near the terminal is slightly higher than that measured near the center of the cell which may be a result of the contact resistance made near the terminals. The temperature measured during cycle fifty-one is slightly higher than that of cycle three because of the higher current, shown earlier in Figure 8.

Figure 9. Cell temperature measured near the terminals and center of the cell during the discharge portion of cycle three and cycle fifty-one respectively. As mentioned earlier, the variable cell was characterized periodically using a 1CCC/CV procedure. Evaluation of the 1C capacity curves recorded during those experiments enables the capacity fade of the cell to be measured. The characterization curves recorded after cycle one and cycle fifty-one respectively are shown in Figure 10. Table 1 documents the capacity extracted during each of the 1C characterization discharge procedures performed on both the variable and control cells. As seen in the figure, the variable cells 1C discharge capacity decreases slightly between cycles one (3.12 Ah) and fifty-one (3.06 Ah). Thus, over a period of fifty-one cycles, in which the cell was loaded in a high rate pulsed fashion, a 1.92% capacity loss is observed.

Comparisons of the 1C characterization data recorded from the control cell shows no measureable evidence of capacity fade after fifty-one cycles.

Figure 10. 1C charge and 1C discharge curves measured from the variable cell after cycles one and cycle fifty-one respectively.
TABLE 1. Usable Capacity (Ah) Measured from Periodic 1C Discharges Performed on the Control and Variable Cells Respectively Cycle 1 12 20 30 51 Variable Cell 3.12 3.12 3.15 3.15 3.06 Control Cell 3.12 3.18 3.16 3.16 3.16

Figures 11 and 12 display the EIS measurements made on the variable and control cells before cycle one and after cycles one, thirty, and fifty-one. As expected, the Nyquist plots contain two semicircles, one at medium frequencies and one at low frequencies. During the initial cycling of a lithium-ion cell, decomposition of the electrolyte occurs and a passive film is formed on the surface of the electrodes. This increases the concentration of lithium-ions in the electrolyte and improves the conductivity of the electrolyte [16]. In the Nyquist plots of both cells, a shift to the left occurs showing that the cells internal impedance is dropping with increasing cycle life due to the increase in electrolyte conductivity. The high frequency inductive tail has been ignored here since the inductance data is not relevant in studying the cycle life of the cell. The medium frequency semicircle represents the passive film present on the electrodes, especially on the cathode. The size of the medium frequency semicircle remains constant as the cycle life of the both variable and control cell increases. This suggests that the thickness of the passive film on the cathode is remaining constant. The low frequency semicircle is representative of the internal charge transfer resistance, both the interfacial and surface film resistances of the cathode and anode. In the EIS plots of the variable cell, shown in Figure 11, the diameter of the low frequency semicircle increases with cycle life indicating an increase in total internal resistance of the cell. The increase in the cells internal resistance explains the mild capacity fade. In the EIS plots of the control cell, seen in Figure 12, it should be noticed that the diameter of the low frequency semicircle remains nearly constant, correlating to no change in the capacity after fifty-one cycles.

Figure 11. EIS data recorded on the variable cell after periodic cycling.

Figure 12. EIS data recorded on the control cell after periodic cycling. Conclusions The work presented here has shown that a high power, 3 Ah LNCAO battery is able to be discharged fifty-one times at an average rate as high as 66C with only a ~1.92% reduction in the usable capacity of the cell. A control cell, cycled at only 1C rates, has shown negligible change in the capacity after the same number of cycles. A novel experimental test stand has been presented which enables researchers to discharge electrochemical cells at extreme elevated rates. It is believed that as cycling continues, the cell will continue to age and that shape changes observed in the EIS curves will reveal trends which can help to predict battery aging mechanisms. Future work involves further cycling in the same manner until more prevalent aging occurs so that trends can be observed.

Acknowledgments This material is based upon work supported by US Office of Naval Research (ONR) under contract number N00014-11-1-0659. The authors would like to express thanks to ONR for their continued support. Any opinions, findings, and conclusions or recommendations expressed in this publication are those of the authors and do not necessarily reflect the views of the US Office of Naval Research. References 1. J.L. Jespersen el al, World Electric Vehicle Journal , 3, Stavanger, Norway (2009). 2. J.B. Goodenough, J. of Power Sources, 174(2), p. 996-1000 (2007). 3. Innovation Environment, General Motors, 2012, http://www.gm.com/vision/greener_vehicles.html, May 16 (2012). 4. Nissan Leaf, Nissan Motor Co. Ltd., 2012, http://www.nissanusa.com/leaf-electriccar/index#/leaf-electric-car/index, May 16 (2012). 5. Ford Hybrids and EVs, Ford Motor Company, Ford Motor Company, http://www.ford.com, May 16 (2012). 6. A. Nourai, IEEE Power and Energy Society General Meeting (2011). 7. G.D. Rodriguez, IEEE Power and Energy Society General Meeting , p. 1 (2010). 8. A. Sitzman, D. Surls, and J. Mallick, Design, IEEE Transactions on Magnetics, 43(1), p. 270 274 (2007). 9. R. Allen and J. Neri, p. 1500 1504, 16th IEEE International Pulsed Power Conference, Albuquerque, New Mexico (2007). 10. C. Nunnally, J.R. Mayes, C.W. Hatfield, and J.D. Dowden, Proceedings of the 17th IEEE International Pulsed Power Conference, p. 930-933, Washington, D.C. (2009). 11. A.J. Dragt, A.J. and J.M Elizondo, Pulsed Power Plasma Science Digest of Technical Papers, 2, p. 1555-1558 (2001). 12. B. Cadilhon, B. Cassany, J.-C. Diot, P. Modin, E. Merle, L. Pecastaing, M. Rivaletto, A. Silvestre de Ferron, and V. Bertrand, IEEE Transactions on Plasma Science, 39, Issue 6, Part 2, p. 1549-1559 (2011). 13. J. Mankowski and M. Kristiansen, IEEE Transactions on Plasma Science, 28 (1), p. 102 108 (2000). 14. B. Shrestha, D.A. Wetz, and P. Novak, IEEE Transactions on Plasma Science, 40(10), Part: 1, p. 2462 2469 (2012). 15. Y. Chen, And A. Sitzman, Pulsed Power Conference, IEEE, p. 485-488 (2005). 16. J. Li, E. Murphy, J. Winnick, And P.A. Kohl, J. of Power Sources (2001). 17. DC Electronic Loads, Chroma Systems Solutions, Inc., http://www.chromausa.com/dcloads.php, April 14 (2012). 18. Arbin Instruments Battery Test Equipment, Arbin Instruments, http://www.arbin.com/products/battery 19. Maccor Battery Test Equipment, Maccor Inc., http://www.maccor.com, April 13 (2012). 20. P. Novak, D.A. Wetz, and B. Shrestha, IEEE Transactions on Plasma Science, 40(10), Part: 1, p. 2416 2424 (2012). 21. D.A. Wetz, B. Shrestha, and P. Novak, Proceedings of the American Society of Naval Engineers 2012 Electric Machines Technology Symposium (EMTS), Philadelphia, Pennsylvania (2012).