Theses Doctoral

Investigating the efficacy of inverse-charging of lead-acid battery electrodes for cycle life and specific energy improvement

Spanos, Constantine

Although competitive today, traditional PbA (<1500 cycles) and advanced lead-acid batteries (ALAB) (>4000 cycles) will not be able to compete with lithium and flow batteries by 2020. To compete with novel zinc, lithium and flow batteries, the PbA chemistry needs to achieve significant performance improvements, primarily through sustainable increases to specific energy (Wh/kg), while not negatively impacting cycle life.
Inverse charging has been examined for its potential in improving PbA cycle life as a battery maintenance procedure, and as a potential technique for improving electrode specific capacity (mAh/kg) during battery manufacturing and formation. A thorough levelized cost of energy (LCOE) shows that for traditional PbA batteries with cycle lives <2000, inverse charging as a maintenance strategy (to increase cycle life) improves battery economics. Inverse charging to increase cycle life for ALAB systems (>4000 cycle life) was proven to worsen battery economics, as additional costs of capital and maintenance fail to outweigh savings achieved through reductions in replacement cost. On the other hand, inverse charging employed as a manufacturing practice to increase specific energy dramatically reduces the cost of the PbA and ALAB systems, ensuring future cost competitiveness. Inverse charging as a maintenance strategy should be restricted to devices with <2000 cycles and to projects with long project lives (20 years) that require frequent replacement. Inverse charging as a manufacturing strategy (to increase specific energy) is highly preferable in all instances.
When successful, inverse charging increases the specific capacity and active material utilization of studied battery electrodes significantly. Successful inverse charging of battery electrodes and pure lead rods show improvements in discharge capacities over a range of discharge rates with negligible impact to coulombic and energy efficiency values. The extent of success, however, depends on several important variables. Thorough examination of inverse charging on Pb rods and porous battery electrodes illustrates the importance of the degree of prior electrode sulfation and obstruction of transport of H₂SO₄. Other important factors include the composition of electrode grid alloys, the peak oxidation voltage applied to the negative electrode during inverse charging, initial particle sizes, and electrolyte additives.
Significant challenges to inverse charging exist. For heavily sulfated batteries and lead metals, impeded electrolyte transport results in excessive internal pore pH increases, creating semipermeable membranes through an electrode hydration mechanism, resulting in dramatic inverse charging failure. Additionally, impedance, voltage, x-ray and BET data hint that post-inverse charging, agglomeration of finely divided Pb and PbSO₄ particles occurs, coupled with negative electrode conductive pathway destruction. As such, the influence of expander materials and nucleation additives should be investigated to better prevent sulfation failure, and to better control the nucleation and growth of lead and lead sulfate structures during inverse charging.
Cycle life studies on flooded lead antimony batteries subjected to periodic inverse charging illustrate that inverse charging is highly successful on all batteries independent of states-of-health. Batteries with poor states-of-health (discharge capacities <15% of initial values) experienced almost perfect discharge capacity restoration post-inverse charging. Traditional methods of extending cycle life (i.e. prolonged overcharging techniques) were demonstrated to be inadequate at appreciably regenerating battery capacities, providing only marginal increases.
The benefits of inverse charging, however, are met with significant challenges to battery redesign. Temporary antimony poisoning effects lead to declines in round-trip-efficiency for batteries with antimony-based positive plates. Tin dissolution results in diminished grid to active material conductivity and reduced capacity for batteries with tin-based positives. For the negative electrode, Brunauer–Emmett–Teller (BET) surface area and x-ray measurements indicate that although large PbSO₄ crystals are oxidized during inverse charging, creating extensive micropore networks during conversion from Pb to PbO₂, surface area and capacity gains are lost during reconversion back to sponge lead due to uncontrolled nucleation and particle fusion. Additionally, active material shedding of the positive and negative electrodes is observed to spike during and after inverse charging. Negative electrode active material suffers excessive degradation and loss of cohesion, particularly for electrodes with small initial particle feature sizes, resulting in a loss of structure upon completion of the technique. Positive electrode composition changes to weakly interconnected b-PbO₂, dramatically increasing electrode capacity while simultaneously accelerating electrode failure through shedding. Loss of particle cohesion in both electrodes promotes excessive shedding and sludging, creating intra-cellular short-circuits. In addition, inverse charging aggravates grid growth, promoting inter-cellular short-circuiting by creating pathways for cell-to-cell electrolyte contact upon seal destruction in current monoblock designs.


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More About This Work

Academic Units
Earth and Environmental Engineering
Thesis Advisors
West, Alan C.
Ph.D., Columbia University
Published Here
January 31, 2017