Publications

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This report describes the status of research being performed under CRADA No. SC10/01771.00 (Lead/Carbon Functionality in VRLA Batteries) between Sandia National Laboratories and East Penn Manufacturing, conducted for the U.S. Department of Energy's Energy Storage Systems Program. The Quarter 1 Milestone was completed on time. The milestone entails conducting a thorough literature review to establish the current level of understanding of the mechanisms through which carbon additions to the negative active material improve valve-regulated lead-acid (VRLA) batteries. Most studies have entailed phenomenological research observing that the carbon additions prevent/reduce sulfation of the negative electrode; however, no understanding is available to provide insight into why certain carbons are successful while others are not. Impurities were implicated in one recent review of the electrochemical behavior of carbon additions. Four carbon samples have been received from East Penn Manufacturing and impurity contents have been analyzed. Carbon has been explored as an addition to lead-acid battery electrodes in a number of ways. Perhaps the most notable to date has been the hybrid 'Ultrabattery' developed by CSIRO where an asymmetric carbon-based electrochemical capacitor is combined with a lead-acid battery into a single cell, dramatically improving high-rate partial-state-of-charge (HRPSoC) operation. As illustrated below, the 'Ultrabattery' is a hybrid device constructed using a traditional lead-acid battery positive plate (i.e., PbO{sub 2}) and a negative electrode consisting of a carbon electrode in parallel with a lead-acid negative plate. This device exhibits a dramatically improved cycle life over traditional VRLA batteries, as well as increased charge power and charge acceptance. The 'Ultrabattery' has been produced successfully by both The Furukawa Battery Co. and East Penn Manufacturing. An example illustrating the dramatic improvement in cycle life of the Ultrabattery over a conventional VRLA battery is shown in the graph.

This report describes the status of research being performed under CRADA No. SC10/01771.00 (Lead/Carbon Functionality in VRLA Batteries) between Sandia National Laboratories and East Penn Manufacturing, conducted for the U.S. Department of Energy's Energy Storage Systems Program. The Quarter 2 Milestone was completed on time. The milestone entails an ex situ analysis of the four carbons that have been added to the negative active material of valve-regulated lead-acid (VRLA) batteries for the purposes of this study. The four carbons selected for this study were a graphitic carbon, a carbon black, an activated carbon, and acetylene black. The morphology, crystallinity, and impurity contents of each of the four carbons were analyzed; results were consistent with previous data. Cycling on a subset of the received East Penn cells containing different carbons (and a control) has been initiated. Carbon has been explored as an addition to lead-acid battery electrodes in a number of ways. Perhaps the most notable to date has been the hybrid 'Ultrabattery' developed by CSIRO where an asymmetric carbon-based electrochemical capacitor is combined with a lead-acid battery into a single cell, dramatically improving high-rate partial-state-of-charge (HRPSoC) operation. As illustrated below, the 'Ultrabattery' is a hybrid device constructed using a traditional lead-acid battery positive plate (i.e., PbO{sub 2}) and a negative electrode consisting of a carbon electrode in parallel with a lead-acid negative plate. This device exhibits a dramatically improved cycle life over traditional VRLA batteries, as well as increased charge power and charge acceptance. The 'Ultrabattery' has been produced successfully by both The Furukawa Battery Co. and East Penn Manufacturing. An example illustrating the dramatic improvement in cycle life of the Ultrabattery over a conventional VRLA battery is shown.

The performance of the Neosonic polymer Li-ion battery was measured using a number of tests including capacity, capacity as a function of temperature, ohmic resistance, spectral impedance, hybrid pulsed power test, utility partial state of charge (PSOC) pulsed cycle test, and an over-charge/voltage abuse test. The goal of this work was to evaluate the performance of the polymer Li-ion battery technology for utility applications requiring frequent charges and discharges, such as voltage support, frequency regulation, wind farm energy smoothing, and solar photovoltaic energy smoothing. Test results have indicated that the Neosonic polymer Li-ion battery technology can provide power levels up to the 10C1 discharge rate with minimal energy loss compared to the 1 h (1C) discharge rate. Two of the three cells used in the utility PSOC pulsed cycle test completed about 12,000 cycles with only a gradual loss in capacity of 10 and 13%. The third cell experienced a 40% loss in capacity at about 11,000 cycles. The DC ohmic resistance and AC spectral impedance measurements also indicate that there were increases in impedance after cycling, especially for the third cell. Cell #3 impedance Rs increased significantly along with extensive ballooning of the foil pouch. Finally, at a 1C (10 A) charge rate, the over charge/voltage abuse test with cell confinement similar to a multi cell string resulted in the cell venting hot gases at about 45°C 45 minutes into the test. At 104 minutes into the test the cell voltage spiked to the 12 volt limit and continued out to the end of the test at 151 minutes. In summary, the Neosonic cells performed as expected with good cycle-life and safety. © 2011 Nova Science Publishers, Inc. All rights reserved.

In this paper the performance of the LiFeBatt Li-ion cell was measured using a number of tests including capacity measurements, capacity as a function of temperature, ohmic resistance, spectral impedance, high power partial state of charge (PSOC) pulsed cycling, pulse power measurements, and an over-charge/voltage abuse test. The goal of this work was to evaluate the performance of the iron phosphate Li-ion battery technology for utility applications requiring frequent charges and discharges, such as voltage support, frequency regulation, and wind farm energy smoothing. Test results have indicated that the LiFeBatt battery technology can function up to a 10C1 discharge rate with minimal energy loss compared to the 1 h discharge rate (1C). The utility PSOC cycle test at up to the 4C1 pulse rate completed 8,394 PSOC pulsed cycles with a gradual loss in capacity of 10 to 15% depending on how the capacity loss is calculated. The majority of the capacity loss occurred during the initial 2,000 cycles, so it is projected that the LiFeBatt should PSOC cycle well beyond 8,394 cycles with less than 20% capacity loss. The DC ohmic resistance and AC spectral impedance measurements also indicate that there were only very small changes after cycling. Finally, at a 1C charge rate, the over charge/voltage abuse test resulted in the cell venting electrolyte at 110 °C after 30 minutes and then open-circuiting at 120 °C with no sparks, fire, or voltage across the cell. © 2011 Nova Science Publishers, Inc. All rights reserved.

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The addition of certain forms of carbon to the negative plate in valve regulated lead acid (VRLA) batteries has been demonstrated to increase the cycle life of such batteries by an order of magnitude or more under high-rate, partial-state-of-charge operation. Such performance will provide a significant impact, and in some cases it will be an enabling feature for applications including hybrid electric vehicles, utility ancillary regulation services, wind farm energy smoothing, and solar photovoltaic energy smoothing. There is a critical need to understnd how the carbon interacts with the negative plate and achieves the aforementioned benefits at a fundamental level. Such an understanding will not only enable the performance of such batteries to be optimzied, but also to explore the feasibility of applying this technology to other battery chemistries. In partnership with the East Penn Manufacturing, Sandia will investigate the electrochemical function of the carbon and possibly identify improvements to its anti-sulfation properties. Shiomi, et al. (1997) discovered that the addition of carbon to the negative active material (NAM) substantially reduced PbSO{sub 4} accumulation in high rate, partial state of charge (HRPSoC) cycling applications. This improved performance with a minimal cost. Cycling applications that were uneconomical for traditional VRLA batteries are viable for the carbon enhanced VRLA. The overall goal of this work is to quantitatively define the role that carbon plays in the electrochemistry of a VRLA battery.

Grid tied PV energy smoothing was implemented by using a valve regulated lead-acid (VRLA) battery as a temporary energy storage device to both charge and discharge as required to smooth the inverter energy output from the PV array. Inverter output was controlled by the average solar irradiance over the previous 1h time interval. On a clear day the solar irradiance power curve is offset by about 1h, while on a variable cloudy day the inverter output power curve will be smoothed based on the average solar irradiance. Test results demonstrate that this smoothing algorithm works very well. Battery state of charge was more difficult to manage because of the variable system inefficiencies. Testing continued for 30-days and established consistent operational performance for extended periods of time under a wide variety of resource conditions. Both battery technologies from Exide (Absolyte) and East Penn (ALABC Advanced) proved to cycle well at a Partial state of charge over the time interval tested.

Grid-tied PV energy smoothing was implemented by using a valve regulated lead-acid (VRLA) battery as a temporary energy storage device to both charge and discharge as required to smooth the inverter energy output from the PV array. Inverter output was controlled by the average solar irradiance over the previous 1h time interval. On a clear day the solar irradiance power curve is offset by about 1h, while on a variable cloudy day the inverter output power curve will be smoothed based on the average solar irradiance. Test results demonstrate that this smoothing algorithm works very well. Battery state of charge was more difficult to manage because of the variable system inefficiencies. Testing continued for 30-days and established consistent operational performance for extended periods of time under a wide variety of resource conditions. Both battery technologies from Exide (Absolyte) and East Penn (Advanced Valve Regulated Lead-Acid) proved to cycle well at a partial state of charge over the time interval tested.

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A comprehensive evaluation and experimental optimization of the FireFly{trademark} 600 off-grid photovoltaic system manufactured by Energia Total, Ltd. was conducted at Sandia National Laboratories in May and June of 2001. This evaluation was conducted at the request of the manufacturer and addressed performance of individual system components, overall system functionality and performance, safety concerns, and compliance with applicable codes and standards. A primary goal of the effort was to identify areas for improvement in performance, reliability, and safety. New system test procedures were developed during the effort.

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