Stability of Electrode-Electrolyte Interfaces during Charging in Lithium Batteries

In this thesis we study the growth of a Li electrode-electrolyte interface in the presence of an elastic prestress. In particular, we focus our interest on Li-air batteries with a solid electrolyte, LIPON, which is a new type of secondary or rechargeable battery. Theoretical studies and experimental evidence show that during the process of charging the battery the replated lithium adds unevenly to the electrode surface. This phenomenon eventually leads to dendrite formation as the battery is charged and discharged numerous times. In order to suppress or alleviate this deleterious effect of dendrite growth, we put forth a study based on a linear stability analysis. Taking into account all the mechanisms of mass transport and interfacial kinetics, we model the evolution of the interface. We find that, in the absence of stress, the stability of a planar interface depends on interfacial diffusion properties and interfacial energy. Specifically, if Herring-Mullins capillarity-driven interfacial diffusion is accounted for, interfaces are unstable against all perturbations of wavenumber larger than a critical value. We find that the effect of an elastic prestress is always to stabilize planar interfacial growth by increasing the critical wavenumber for instability. A parametric study results in quantifying the extent of the prestress stabilization in a manner that can potentially be used in the design of Li-air batteries. Moreover, employing the theory of finite differences we numerically solve the equation that describes the evolution of the surface profile and present visualization results of the surface evolution by time. Lastly, numerical simulations performed in a commercial finite element software validate the theoretical formulation of the interfacial elastic energy change with respect to the planar interface.

Nano-polypyrrole supercapacitor arrays prepared by layer-by-layer assembling method in anodic aluminum oxide templates

A novel method for preparing nano-supercapacitor arrays, in which each nano-supercapacitor consisted of electropolymerized Polypyrrole (PPy) electrode / porous TiO2 separator / chemical polymerized PPy electrode, was developed in this paper. The nano-supercapacitors were fabricated in the nano array pores of anodic aluminum oxide template using the bottom-up, layer-by-layer synthetic method. The nano-supercapacitor diameter was 80 nm, and length 500 nm. Based on the charge/discharge behavior of nano-supercapacitor arrays, it was found that the PPy/TiO2/PPy array supercapacitor devices performed typical electrochemical supercapacitor behavior. The method introduced here may find application in manufacturing nano-sized electrochemical power storage devices in the future for their use in the area of microelectronic devices and microelectromechanical systems.

Variations in eastern North Pacific demersal fish biomass based on the U.S. west coast groundfish bottom trawl survey (2003–2010)

In response to declining biomass of Northeast Pacific groundfish in the late 1990s and to improve the scientific basis for management of the fishery, the Northwest Fisheries Science Center standardized and enhanced their annual bottom trawl survey in 2003. The survey was expanded to include the entire area along the U.S. west coast at depths of 55–1280 m. Coast-wide biomass and species richness significantly decreased during the first eight years (2003–10) of this fishery-independent survey. We observed an overall tendency toward declining biomass for 62 dominant taxa combined (fishery target and nontarget species) and four of seven subgroups (including cartilaginous fish, flatfishes, shelf rockfishes, and other shelf species), despite increasing or variable biomass trends in individual species. These decreases occurred during a period of reduced catch for groundfish along the shelf and upper slope regions relative to historical rates. We used information from multiple stock assessments to aggregate species into three groups: 1) with strong recruitment, 2) without strong recruitment in 1999, and 3) with unknown recruitment level. For each group, we evaluated whether declining biomass was primarily related to depletion (using year as a proxy) or environmental factors (i.e., variation in the Pacific Decadal Oscillation). According to Akaike’s information criterion, changes in aggregate biomass for species with strong recruitment were more closely related to year, whereas those with no strong recruitment were more closely related to climate. The significant decline in biomass for species without strong recruitment confirms that factors other than depletion of the exceptional 1999 year class may be responsible for the observed decrease in biomass along the U.S. west coast.

Comparison of habitat-based indices of abundance with fishery-independent biomass estimates from bottom trawl surveys

Rockfish species are notoriously difficult to sample with multispecies bottom trawl survey methods. Typically, biomass estimates have high coefficients of variation and can fluctuate outside the bounds of biological reality from year to year. This variation may be due in part to their patchy distribution related to very specific habitat preferences. We successfully modeled the distribution of five commercially important and abundant rockf ish species. A two-stage modeling method (modeling both presence-absence and abundance) and a collection of important habitat variables were used to predict bottom trawl survey catch per unit of effort. The resulting models explained between 22% and 66% of the variation in rockfish distribution. The models were largely driven by depth, local slope, bottom temperature, abundance of coral and sponge, and measures of water column productivity (i.e., phytoplankton and zooplankton). A year-effect in the models was back-transformed and used as an index of the time series of abundance. The abundance index trajectories of three of five species were similar to the existing estimates of their biomass. In the majority of cases the habitat-based indices exhibited less interannual variability and similar precision when compared with stratified survey-based biomass estimates. These indices may provide for stock assessment models a more stable alternative to current biomass estimates produced by the multispecies bottom trawl survey in the Gulf of Alaska.

Changes in a benthic megafaunal community due to disturbance from bottom fishing and the establishment of a fishery closure

Trawling and dredging on Georges Bank (northwest Atlantic Ocean) have altered the cover of colonial epifauna, as surveyed through in situ photography. A total of 454 photographs were analyzed from areas with gravel substrate between 1994 and 2000 at depths of 40–50 m and 80–90 m. The cover of hydroids, bushy bryozoans, sponges, and tubeworms was generally higher at sites undisturbed by fishing than at sites classified as disturbed. The magnitude and significance of this effect depended on depth and year. Encrusting bryozoans were the only type of colonial epifauna positively affected by bottom fishing. Species richness of noncolonial epifauna declined with increased bottom fishing, but Simpson’s index of diversity typically peaked at intermediate levels of habitat disturbance. Species that were more abundant at undisturbed sites possessed characteristics that made them vulnerable to bottom fishing. These characteristics include emergent growth forms, soft body parts, low motility, use of complex microhabitats, long life spans, slow growth, and larval dispersal over short distances. After the prohibition of bottom fishing at one site, both colonial and noncolonial species increased in abundance. Populations of most taxa took two years or more to increase after the fishing closure. This finding indicates that bottom fishing needs to be reduced to infrequent intervals to sustain the benthic species composition of Georges Bank at a high level of biodiversity and abundance.

The relationships between fish assemblages and the amount of bottom horizontal beam exposed at California oil platforms: fish habitat preferences at man-made platforms and (by inference) at natural reefs

Between 1995 and 2002, we surveyed fish assemblages at seven oil platforms off southern and central California using the manned research submersible Delta. At each platform, there is a large horizontal beam situated at or near the sea floor. In some instances, shells and sediment have buried this beam and in other instances it is partially or completely exposed. We found that fish species responded in various ways to the amount of exposure of the beam. A few species, such as blackeye goby (Rhinogobiops nicholsii), greenstriped rockfish (Sebastes elongatus), and pink seaperch (Zalembius rosaceus) tended to avoid the beam. However, many species that typically associate with natural rocky outcrops, such as bocaccio (S. paucispinis), cowcod (S. levis), copper (S. caurinus), greenblotched (S. rosenblatti), pinkrose (S. simulator) and vermilion (S. miniatus) rockfishes, were found most often where the beam was exposed. In particular, a group of species (e.g., bocaccio, cowcod, blue (Sebastes mystinus), and vermilion rockfishes) called here the “sheltering habitat” guild, lived primarily where the beam was exposed and formed a crevice. This work demonstrates that the presence of sheltering sites is important in determining the species composition of man-made reefs and, likely, natural reefs. This research also indicates that adding structures that form sheltering sites in and around decommissioned platforms will likely lead to higher densities of many species typical of hard and complex structure.

Results of bottom trawl surveys carried out in Vietnamese waters (20-200 m) in 1996-1997

Bottom trawl surveys were conducted in the southwest monsoon season in 1996 (survey 1) and in the northeast monsoon season in 1996-97 (survey 2) throughout Vietnamese waters. The surveys mainly covered the depth zone 50-200 m but in the northeast monsoon season the depth zone 20-50 m was included in the northern and southern areas. Overall, 273 trawl hauls were conducted. The total biomass for Vietnamese waters in the depth zone 20-200 m was estimated at 700 000 t . Biomass estimates are given for the most abundant species. A relatively higher mean catch-per-unit effort (CPUE) was obtained from survey 2 than from survey 1 and in partcular at depth ranges 50-100 and 100-200 m in south Vietnam. Overall, the dominant families were Monacanthidae (34%), Carangidae (15%), Trichiuridae (9%) and Synodontidae (6%).

Length-weight relationships of soft-bottom demersal fishes from Jalisco and Colima states, Mexico

The parameters a and b of the length-weight relationship of the form W=aL super(b) were estimated for 24 species of soft bottom demersal fishes caught on the continental shelf off Jalisco and Colima states, Mexico. The estimates of b ranged from 2.74 to 3.33. The mean of the b values is 3.02 with a standard deviation of 0.15.

Descriptions of the U.S. Gulf of Mexico Reef Fish Bottom Longline and Vertical Line Fisheries Based on Observer Data

In July 2006, a mandatory observer program was implemented to characterize the commercial reef fish fishery operating in the U.S. Gulf of Mexico. The primary gear types assessed included bottom longline and vertical line (bandit and handline). A total of 73,205 fish (183 taxa) were observed in the longline fishery. Most (66%) were red grouper, Epinephelus morio, and yellowedge grouper, E. flavolimbatus. In the vertical line fishery, 89,015 fish (178 taxa) were observed of which most (60%) were red snapper, Lutjanus campechanus, and vermilion snapper, Rhomboplites aurorubens. Based on surface observations of discarded under-sized target and unwanted species, the majority of fish were released alive; minimum assumed mortality was 23% for the vertical line and 24% for the bottom longline fishery. Of the individuals released alive in the longline fishery, 42% had visual signs of barotrauma stress (air bladder expansion/and or eyes protruding). In the vertical line fishery, 35% of the fish were released in a stressed state. Red grouper and red snapper size composition by depth and gear type were determined. Catch-per-unit-effort for dominant species in both fisheries, illustrated spatial differences in distribution between the eastern and western Gulf. Hot Spot Analyses for red grouper and red snapper identified areas with significant clustering of high or low CPUE values.

Fishery-independent Bottom Trawl Surveys for Deep-water Fishes and Invertebrates of the U.S. Gulf of Mexico, 2002–08

From 2002 through 2008, the Mississippi Laboratories of the NMFS Southeast Fisheries Science Center, NOAA, conducted fishery-independent bottom trawl surveys for continental shelf and outer-continental shelf deep-water fishes and invertebrates of the U.S. Gulf of Mexico (50–500 m bottom depths). Five-hundred and ninety species were captured at 797 bottom trawl locations. Standardized survey gear and randomly selected survey sites have facilitated development of a fishery-independent time series that characterizes species diversity, distributions, and catch per unit effort. The fishery-independent surveys provide synoptic descriptions of deep-water fauna potentially impacted by various anthropogenic factors.

Temporal and Spatial Distribution of Finfish Bycatch in the U.S. Atlantic Bottom Longline Shark Fishery

Bycatch in U.S. fisheries has become an increasingly important issue to both fisheries managers and the public, owing to the wide range of marine resources that can be involved. From 2002 to 2006, the Commercial Shark Fishery Observer Program (CSFOP) and the Shark Bottom Longline Observer Program (SBLOP) collected data on catch and bycatch caught on randomly selected vessels of the U.S. Atlantic shark bottom longline fishery. Three subregions (eastern Gulf of Mexico, South Atlantic, Mid-Atlantic Bight), five years (2002–06), four hook types (small, medium, large, and other), seven depth ranges (<50 m to >300 m), and eight broad taxonomic categories (e.g. Selachimorpha, Batoidea, Serranidae, etc.) were used in the analyses. Results indicated that the majority of bycatch (number) was caught in the eastern Gulf of Mexico and that the Selachimorpha taxon category made up over 90% of the total bycatch. The factors year followed by depth were the most common significant factors affecting bycatch.

History of Alaska Red King Crab, Paralithodes camtschaticus, Bottom Trawl Surveys, 1940–61

Thirteen bottom trawl surveys conducted in Alaska waters for red king crab, Paralithodes camtschaticus, during 1940–61 are largely forgotten today even though they helped define our current knowledge of this resource. Government publications on six exploratory surveys (1940–49, 1957) included sample locations and some catch composition data, but these documents are rarely referenced. Only brief summaries of the other seven annual (1955–61) grid-patterned trawl surveys from the eastern Bering Sea were published. Although there have been interruptions in sampling and some changes in the trawl survey methods, a version of this grid-patterned survey continues through the present day, making it one of the oldest bottom-trawl surveys in U.S. waters. Unfortunately, many of the specific findings made during these early efforts have been lost to the research community. Here, we report on the methods, results, and significance of these early surveys, which were collated from published reports and the unpublished original data sheets so that researchers might begin incorporating this information into stock assessments, ecosystem trend analyses, and perhaps even revise the baseline population distribution and abundance estimates.