The relationship of capillary pressure to liquid saturation for the water–air fluid pair in two different types of gas diffusion media (GDM) used in polymer electrolyte membrane fuel cell (PEMFC) electrodes is elucidated. It is experimentally demonstrated that GDM samples with and without treatment with poly(tetrafluoroethylene) (PTFE) ubiquitously display permanent capillary pressure hysteresis. Water does not imbibe spontaneously into a dry GDM, neither is it ejected spontaneously from a water-saturated GDM. Rather, positive displacement pressure is required to force both water and air into GDMs, whereas the main effect of adding PTFE is to increase the amount of work required for forcing water into the GDM, and to decrease the work required for water removal. Irrespective of PTFE content, the GDM samples tested are generally shown to behave as materials of intermediate (neutral) wettability. The US Bureau of Mines (USBM) wettability index nevertheless shows that water is the preferentially non-wetting phase in PTFE-treated GDMs and the preferentially wetting phase in untreated GDMs. Water–air capillary pressure curves are found to depend on sample thickness, clearly demonstrating that finite size effects are important. Finally, compression of the GDM is found to increase the capillary pressures for water injection and decrease the capillary pressures required for water withdrawal. These results should aid the design of GDMs with improved water management properties and the modeling of PEMFC electrodes in general.
The calendar life of a commercial graphite/NMC-LMO lithium-ion battery is assessed under various storage temperature (35°C and 60°C) and state-of-charge (0% and 100%) conditions. Virtually no degradation is observed for cells stored at 0% SOC as expected, whereas those aged for 9 months in a fully charged state at 35°C and 60°C lose ∼10% and ∼43% of their capacity, respectively. Differential-voltage analysis of periodic cell cycling data and post-mortem examination of the aged electrodes are used to identify degradation modes. Three main sources of high-temperature capacity loss are identified: i) electrode dry-out due to gas formation (∼30%), ii) loss of cyclable lithium (∼10%) and iii) cathode active material loss (∼3%). Cells stored at a lower temperature of 35°C experience little gas generation and degrade primarily through the loss of Li inventory. The analysis shows that similar amounts of cyclable Li are consumed by side reactions during calendar aging at both storage temperatures of 35°C and 60°C. Non-destructive compression (1.0–5.0 psi) of the aged pouch cells during discharge is shown to improve their capacity by ∼15%. This effect is attributed to the redistribution of gas bubbles inside the pouch cell by the applied pressure.
Ionic-complementary peptides are novel nano-biomaterials with a variety of biomedical applications including potential biosurface engineering. This study presents evidence that a model ionic-complementary peptide EAK16-II is capable of assembling/coating on hydrophilic mica as well as hydrophobic highly ordered pyrolytic graphite (HOPG) surfaces with different nano-patterns. EAK16-II forms randomly oriented nanofibers or nanofiber networks on mica, while ordered nanofibers parallel or oriented 60° or 120° to each other on HOPG, reflecting the crystallographic symmetry of graphite (0001). The density of coated nanofibers on both surfaces can be controlled by adjusting the peptide concentration and the contact time of the peptide solution with the surface. The coated EAK16-II nanofibers alter the wettability of the two surfaces differently: the water contact angle of bare mica surface is measured to be <10°, while it increases to 20.3±2.9° upon 2 h modification of the surface using a 29 µM EAK16-II solution. In contrast, the water contact angle decreases significantly from 71.2±11.1° to 39.4±4.3° after the HOPG surface is coated with a 29 µM peptide solution for 2 h. The stability of the EAK16-II nanofibers on both surfaces is further evaluated by immersing the surface into acidic and basic solutions and analyzing the changes in the nanofiber surface coverage. The EAK16-II nanofibers on mica remain stable in acidic solution but not in alkaline solution, while they are stable on the HOPG surface regardless of the solution pH. This work demonstrates the possibility of using self-assembling peptides for surface modification applications.
1 January 2010 in Journal of the Electrochemical Society
The breakthrough conditions (capillary pressure and liquid water saturation) in a fibrous gas diffusion medium (GDM) used in polymer electrolyte membrane (PEM) fuel cell electrodes have been studied experimentally by two independent techniques and numerically by pore network modeling. Experiments show that treatment of the GDMs with a hydrophobic polymer coating reduces the water saturation at a breakthrough by 50%. Invasion percolation modeling is employed to simulate the breakthrough process and to determine mass-transfer rates through the partially saturated network. This model shows that the water saturation at breakthrough is drastically reduced when a microporous layer (MPL) is incorporated into the GDM, agreeing with experiments. However, the simulations yield limiting currents significantly higher than those observed in practice whether or not an MPL is present. Further calculations to include the contribution of condensation to water saturation within the GDM also result in unrealistically high limiting currents and suggest that mass-transfer resistance in the catalyst layer that is not included in the model plays an important role. If condensation is the principal mode for water accumulation within the GDM, simulations show that the MPL has only a small impact on liquid water distribution and does not improve performance, contrary to expectation.
9 September 2014 in Physical Chemistry Chemical Physics
The proposed model describes the lithiation–delithiation dynamics of LiFePO4 electrodes and is capable of simultaneously explaining various unusual behaviors observed for this phase transition material.