Evaluation of High Power Energy Storage Devices for Use in Compact Pulsed Power Systems

Biju Shrestha, Peter Novak, and David Wetz (PhD) University of Texas at Arlington College of Engineering Electrical Engineering Department 416 Yates Street 537 Nedderman Hall Arlington, Texas 76019-0016 biju.shrestha@mavs.uta.edu

Motivation
High density energy storage is needed for driving naval pulsed power applications Electrochemical energy storage devices have either possessed a high energy density or a high power density, but not both Advancement in the development of electrode materials and electrolytes has helped to increase energy density and power density in electrochemical cells. These higher densities allow them to drive fast, high current pulsed power applications We seek to discover the aging and power limitations of high power cells when they are discharged repeatedly at elevated rates (tens to hundreds of times their rated C values)

JM Energy Lithium Ion Capacitor Presentation, ULTIMO, http://www.jmenergy.co.jp/en/product.html, JM Energy Corporation, Copyright(C), July 2010.

Pulsed Power
100 ms pulsed discharge
Current normalized to cell mass Power normalized to cell mass

Ragone chart comparison of the 1C energy density and the 100 ms pulsed power density

High C Rate Pulsed Applications

The ability to source high C pulsed currents makes them potential prime power sources for applications such as
Compact Marx Generators Laser Systems EM Launchers Seed Current Sources Grid energy storage Hybrid/electric vehicles
Architecture
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Lithium-Ion Battery Aging

Much research has been done to understand the physical processes that occur inside of lithium-ion batteries as they are cycled and aged at their nominal power rating. On the negative electrode side, the main parameters are SEI layer stability, SEI structure/composition and polluting agents. On the positive electrode side, the key factors seem to be material structure evolution and organic solvent oxidation[1],[2]. The development of very high power Li-ion cells is still quite recent and, to our knowledge, there have been no documented research efforts detailing the effect extremely elevated discharge rate cycling has on capacity and power fade. This research attempts to study the effect of very high rate pulsed discharge (> 80C, 50% duty cycle 10 kHz) coupled with 1C charge rate, at room temperature without added cooling to the cells.
[1] [2] Guy Sarre, Ph Blanchard, M. Broussely, Aging of Lithium-ion batteries, Journal of Power Sources, 127 (2004) 65-71. M. Broussely, Ph. Biensan, F. Bonhomme, Ph. Blanchard, S. Herreyre, K. Nechev, R.J. Staniewicz, Main aging mechanisms in Li ion batteries, Journal of Power Sources, 146 (2005), 90-96.

EIS Study of Lithium-ion Batteries

Impedance spectra of fully discharged lithium-ion batteries with different cycle numbers at a 1C rate: (a) 0; (b) 40; (c) 286 cycles. Source: J. Li, E. Murphy, J. Winnick, And P.A. Kohl, Studies on the cycle life of commercial 6 lithium ion batteries during rapid charge-discharge cycle, Journal of Power Sources, 2001.

High C Pulsed load

Designed to discharge up to 10 kA peak pulsed current 10 kHz switching frequency Variable inductance loop to adjust the discharge rise time Can be easily modified to achieve lower (more standard) discharge rates if needed Incorporates several safety features in the event of thermal runaway

Data Acquisition
Cell voltage is monitored using a differential probe. Cell current is monitored using both a Rogowski coil and custom current viewing resistor (CVR). National instrument data acquisition system (PXIe-6361) is used with BNC-2110 connector. Temperature data is collected using a 0.076 mm K-type thermocouple and 16 channel NI-9213 thermocouple module in a cDAQ-9171 (up to 100 S/s for one channel). Metrohm PGSTAT 302N/FRA Potentiostat with 20 A Current booster is connected.

Experimental Setup

Experimental cell
Two Saft 3Ah LiNixCOyAl1-x-yO2 (NCA) cells are used:
One is the control cell subjected to standard 1C charge / discharge. Another is the variable cell subjected to high C pulsed loading.

Cell chosen due to its:

Low ESR (~1.5m) Low capacity allows for quicker testing Scalability to larger cells of similar chemistry 3Ah Cell Properties
Capacity 3Ah Weight .21kg Continuous Discharge Power 17.3 kW/kg Specific Energy 71 Wh/kg Measured ESR ~1.5m
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Experimental Test Plan

Elevated Discharge*
3 A CC charge to 4.1 V 4.1 V CV charge until current decreases to 0.3A

1C Characterization*
3 A CC charge to 4.1 V 4.1 V CV charge until 0.3 A

Charge

Charge

EIS

Frequency sweep from 10 kHz to 10 mHz 10 mV sinusoidal amplitude

Discharge

10 kHz discharge at 50% duty cycle until cell voltage reaches 2.0 V

3 A CC discharge to 3.0 V Discharge 3.0 V CV discharge until 0.3 A Frequency sweep from 10 kHz to 10 mHz 10 mV sinusoidal amplitude
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*Cell starts at 0% state of charge (SOC) (3.0V) CC = constant current CV = constant voltage

EIS

Metrics for Investigation

Cell voltage, current, and temperature Capacity measurement is performed through integrating current with respect to time (Coulomb Counting) Electrochemical Impedance Spectroscopy (EIS) is used to measure changes in the internal resistance. Attempts are being made to correlate these changes to physical changes inside the cell.
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Experiment performed
1C Cell Characterization Cycle = 1 1C Cell Characterization Cycle = 2

Increase Cycle by 1

Increase Cycle by 1

Elevated Discharge of Cell

1C Rated Cycle

Is Cycle=10?

Is Cycle=10?

Variable Cell (201 cycles completed)

Controlled Cell 13 (97 cycles completed)

Profiles: Current and Voltage

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Temperature Profile
The graph describes the temperature profiles recorded during the 3rd and 201st elevated pulsed discharge experiments performed at room temperature. Elevated discharge in cycle 3 took 140 seconds and in cycle 201 took 120 seconds due to combined effects of increased conductivity at higher cell temperature and decrease in cell capacity. Room temperature during cycle 201 was approximately 4C higher than cycle 3.

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1C Discharge Capacity After Elevated Pulsed Discharge

Voltage vs. Capacity recorded from the variable test cell during the periodic 1C discharge procedure There is a decrease in cell capacity with increasing cycle number It is important to note that as of now this data is representative of only one, research grade, lithium-ion cell Repeat experiments are needed to confirm repeatability Capacity measurements of both the variable and control cells 12.70% capacity loss was measured in variable cell after 200 cycles. No capacity loss was measured in the control cell after 97 cycles.
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Electrochemical Impedance Spectroscopy Result for variable cell

Prior to cycle 50, the cells conductivity increased as a result of the cell settling in After cycle 50, the conductivity started to decrease as the cell started to age The medium frequency semicircle is decreasing slowly, which represents the increase in passive film formation on the electrodes, especially on the cathode. The low frequency semicircle represents the internal charge transfer resistance (both the interfacial and surface film resistances of the cathode and anode). The diameter of the low frequency semicircle is increasing with cycle life, indicating an increase in total internal resistance of the cell.

Nyquist plots of baseline at 100% SOC

EIS Setup Parameters Frequency: 20kHz to 10mHz Amplitude: 10mV OCP: 4.10V

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Conclusions
Two Saft 3 Ah NCA lithium-ion cells are being cycled. The variable cell has been cycled 201 times Discharge performed in a pulsed elevated fashion with roughly 83C peak currents at a frequency of 10 kHz with a 50% duty cycle. Recharge was performed using a 1C constant current - constant voltage procedure. Control cycle has been cycled 97 times at 1C. Roughly 12.70% capacity fade has been observed in the variable cell. No capacity fade has been observed on the control cell. EIS measurements are being used to correlate the aging of the cell to physical changes internally. The cells will continue to be cycled until 20% capacity fade is observed in the same fashion to better understand the rate of capacity fade at higher C rates. It is again important to note that as of now this data is representative of only one, research grade, lithium-ion cell and that more work is needed to demonstrate repeatability
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ACKNOWLEDGEMENTS
Comprehensive College of Engineering in North Texas