Electrochemical characterization of poly(ethylene oxide)- zinc chloride system and its application in rechargeable batteries

The system PEOnZnCl2 with n=4-16 was studied in view of its potential application in a solid state rechargeable zinc battery. A.c. conductivity and cationic transference number measurements, in the temperature range 20-150ºC, were performed and the electrochemical stability window was established for the polymer electrolyte with n=4 composition. The ionic conductivity, σ, of this film, follows a VTF behaviour, with an activation energy of 3.3 ± 0.2 kJ mol-1 and σ values were found between 2.50x10-7 S cm-1 at 24ºC and 4.81x10-4 S cm-1 at 145ºC. Acceptable zinc ion transference numbers of 0.36 (medium value) and decomposition voltage values between 3.19V (20ºC) and 1.44V (150ºC) were estimated. Cyclic voltammetric studies using Zn/PEO4ZnCl2/Zn cell indicated reversibility of the Zn/Zn2+ couple at the electrode/electrolyte interface. Several cells Zn(-)/PEO4ZnCl2/Nb2O5(+) were assembled and studied at 55ºC, with several discharge current densities. Results of cell’s discharge profiles, capacity values, charge-discharge cycles behaviour and stability are reported

Characterisation and performance studies of a LiFePO4 cathode material synthesized by microwave heating

Lithium iron phosphate with incorporated carbon, LiFePO4-C, was synthesized by the microwave-assisted method. X-ray diffraction analyses showed higher crystallization degrees for samples submitted to higher irradiation times. A particle-agglomerated morphology was associated as revealed by scanning electron microscopy. The electrochemical character-istics of a composite cathode containing the synthesized product were evaluated. The two-phase electrochemical process between FePO4 and LiFePO4 was evidenced in the cycling voltammogram profile and its reversibility and stability were demonstrated. An additional redox reversible reaction was revealed and assigned to another phosphate present in the synthesized product. The charge/discharge performance study indicated a good capacity retention after the initial cy-cles where capacity fading was associated to the resistance of a SEI film that forms and grows on the cathode’s surface. Results obtained by electrochemical impedance analysis before and after cell’s cycling are discussed

EIS diagnostics of aged Li-ion batteries

High-power batteries with long cycling life and adequate storage behaviour are needed as energy sources devices for (hybrid) electric vehicles and lithium-ion rechargeable cells are the most promising candidates. In this work, Li-ion cells with a nominal capacity of 10 Ah were studied. Electrochemical impedance spectroscopy (EIS) was used for studying the cycling ageing effect on discharge capacity fade. EIS measurements were conducted in a galvanostatic mode, by means of a Solartron Electrochemical Interface 1286 and a Solartron FRA 1250 controlled by Zplot from Scribner Associates. Scanning frequency ranged from 600 Hz to 0.005 Hz and the ac amplitude was set to 100 mA. An equivalent circuit complex non-linear least squares fitting procedure was used for spectra analyses. Cell charge transfer and film resistances were estimated at several cycle life stages and its evolution on cycle number was analysed. Capacity losses were estimated after 300, 600 and 1200 cycles at C/1 discharge rate and were found to be 5.8, 7.5 and 16.8% of the initial capacity, respectively. EIS data revealed that the major factor responsible for the observed capacity fade was the cell’s charge transfer resistance (Rct) increase following the opposite tendency of the discharge capacity values with cycle number. Very little change can be attributed to film resistances as a result of ageing by cycling. The SEI layer thickness appeared to increase from 0 to 300 cycles remaining almost constant up to 1200 cycles. The effect of a high storage temperature on the performance of the sealed commercial batteries was evaluated by means of discharge capacity measurements and impedance behaviour. The thermal ageing conditions were applied over time and the results were interpreted taking into account the cell’s state of charge (SOC). Before storage at 45 oC, in an open circuit state, cells were fully charged (100% SOC). At defined intervals, cells were cooled to ambient temperature and capacities were determined by a discharge step. As the cells aged up to 25 weeks at 45 oC, the C/1 capacity slowly fades, at first, with a capacity retention of about 95% after 16 weeks of storage. However, the value of discharge capacity loss reached 10.9%, after 25 weeks (Fig. 1). Impedance data were fit to an equivalent circuit with a high frequency arc associated to the SEI film resistance (R sei) and a second arc at medium frequencies to Rct

Degradation of lithium Iron phosphate-based cathode in lithium-ion batteries: a post-mortem analysis

Commercial Li-ion batteries were studied in view to investigate the degradation of the positive electrode in an end-of-life battery condition. Post-mortem analyses were performed by using SEM and DRX techniques; structural and morphological changes after prolonged cycling were evaluated comparatively to a fresh cathode sample. The cycling procedure based on a constant current (CC)/constant voltage (CV) charge and CC discharge was executed, being the condition of end-of-life battery achieved after submitting the Li-ion battery to nearly 2000 charge/discharge cycles. EDS analysis revealed zirconium element as the dopant of a LiFePO4-based cathode of the battery under study. According to X-ray diffraction results for the fresh (charged condition) cathode, the positive electrode includes in its constitution a mixture of crystalline compounds, LiFePO4 and FePO4. SEM images displayed and DRX patterns obtained for the cycled cathode showed modifications compared to the fresh cathode results, evidencing the degradation of the battery at the end-of-life: decrease in the density of microparticles associated to areas where the insertion/de-insertion occurs; decrease of the LiFePO4/FePO4 ratio; both results pointed out to the occurrence of battery loss capacity with the imposed charge/discharge cycles

The effect of chloride as catalyst layer contaminant on the degradation of PEMFCs

In this work, the effect of chloride as a catalyst contaminant was studied on the performance and durability of a low power open-cathode fuel cell, intended for passive management of water. In an ex-situ study, cyclic voltammetry was used to assess the redox behaviour of platinum in chloride contaminated solutions at room temperature.The cell was operated integrating a range of relative humidity (RH) from ~30 to 80% and temperatures from 5 to 55 ºC. Results indicated that 60% RH is associated to maximum fuel cell performance over the studied temperature range. An examination of the fuel cell components after 100 h of operation revealed that chloride contamination has produced cathode failure associated to catalyst migration favored by operation conditions that allowed platinum particles to break free from their carbon backing and migrate toward the polymer electrolyte. Migration resulted in precipitation with larger mean particle size distribution within the solid electrolyte when compared to the original catalyst layer, rendering a very significant loss of thickness in the cathode material

Characterizing partial AZFc deletions of the Y chromosome with amplicon-specific sequence markers

BACKGROUND: The AZFc region of the human Y chromosome is a highly recombinogenic locus containing multi-copy male fertility genes located in repeated DNA blocks (amplicons). These AZFc gene families exhibit slight sequence variations between copies which are considered to have functional relevance. Yet, partial AZFc deletions yield phenotypes ranging from normospermia to azoospermia, thwarting definite conclusions on their real impact on fertility. RESULTS: The amplicon content of partial AZFc deletion products was characterized with novel amplicon-specific sequence markers. Data indicate that partial AZFc deletions are a male infertility risk [odds ratio: 5.6 (95% CI: 1.6-30.1)] and although high diversity of partial deletion products and sequence conversion profiles were recorded, the AZFc marker profiles detected in fertile men were also observed in infertile men. Additionally, the assessment of rearrangement recurrence by Y-lineage analysis indicated that while partial AZFc deletions occurred in highly diverse samples, haplotype diversity was minimal in fertile men sharing identical marker profiles. CONCLUSION: Although partial AZFc deletion products are highly heterogeneous in terms of amplicon content, this plasticity is not sufficient to account for the observed phenotypical variance. The lack of causative association between the deletion of specific gene copies and infertility suggests that AZFc gene content might be part of a multifactorial network, with Y-lineage evolution emerging as a possible phenotype modulator

Characterizing partial AZFc deletions of the Y chromosome with amplicon-specific sequence markers

BACKGROUND: The AZFc region of the human Y chromosome is a highly recombinogenic locus containing multi-copy male fertility genes located in repeated DNA blocks (amplicons). These AZFc gene families exhibit slight sequence variations between copies which are considered to have functional relevance. Yet, partial AZFc deletions yield phenotypes ranging from normospermia to azoospermia, thwarting definite conclusions on their real impact on fertility. RESULTS: The amplicon content of partial AZFc deletion products was characterized with novel amplicon-specific sequence markers. Data indicate that partial AZFc deletions are a male infertility risk [odds ratio: 5.6 (95% CI: 1.6–30.1)] and although high diversity of partial deletion products and sequence conversion profiles were recorded, the AZFc marker profiles detected in fertile men were also observed in infertile men. Additionally, the assessment of rearrangement recurrence by Y-lineage analysis indicated that while partial AZFc deletions occurred in highly diverse samples, haplotype diversity was minimal in fertile men sharing identical marker profiles. CONCLUSION: Although partial AZFc deletion products are highly heterogeneous in terms of amplicon content, this plasticity is not sufficient to account for the observed phenotypical variance. The lack of causative association between the deletion of specific gene copies and infertility suggests that AZFc gene content might be part of a multifactorial network, with Y-lineage evolution emerging as a possible phenotype modulator

Identification of differential gene expression in in vitro FSH treated pig granulosa cells using suppression subtractive hybridization

FSH, which binds to specific receptors on granulosa cells in mammals, plays a key role in folliculogenesis. Its biological activity involves stimulation of intercellular communication and upregulation of steroidogenesis, but the entire spectrum of the genes regulated by FSH has yet to be fully characterized. In order to find new regulated transcripts, however rare, we have used a Suppression Subtractive Hybridization approach (SSH) on pig granulosa cells in primary culture treated or not with FSH. Two SSH libraries were generated and 76 clones were sequenced after selection by differential screening. Sixty four different sequences were identified, including 3 novel sequences. Experiments demonstrated the presence of 25 regulated transcripts. A gene ontology analysis of these 25 genes revealed (1) catalytic; (2) transport; (3) signal transducer; (4) binding; (5) anti-oxidant and (6) structural activities. These findings may deepen our understanding of FSH's effects. Particularly, they suggest that FSH is involved in the modulation of peroxidase activity and remodelling of chromatin

The AZFc region of the Y chromosome: at the crossroads between genetic diversity and male infertility

BACKGROUND: The three azoospermia factor (AZF) regions of the Y chromosome represent genomic niches for spermatogenesis genes. Yet, the most distal region, AZFc, is a major generator of large-scale variation in the human genome. Determining to what extent this variability affects spermatogenesis is a highly contentious topic in human reproduction. METHODS: In this review, an extensive characterization of the molecular mechanisms responsible for AZFc genotypical variation is undertaken. Such data are complemented with the assessment of the clinical consequences for male fertility imputable to the different AZFc variants. For this, a critical re-evaluation of 23 association studies was performed in order to extract unifying conclusions by curtailing methodological heterogeneities. RESULTS: Intrachromosomal homologous recombination mechanisms, either crossover or non-crossover based, are the main drivers for AZFc genetic diversity. In particular, rearrangements affecting gene dosage are the most likely to introduce phenotypical disruptions in the spermatogenic profile. In the specific cases of partial AZFc deletions, both the actual existence and the severity of the spermatogenic defect are dependent on the evolutionary background of the Y chromosome. CONCLUSIONS: AZFc is one of the most genetically dynamic regions in the human genome. This property may serve as counter against the genetic degeneracy associated with the lack of a meiotic partner. However, such strategy comes at a price: some rearrangements represent a risk factor or a de-facto causative agent of spermatogenic disruption. Interestingly, this precarious balance is modulated, among other yet unknown factors, by the evolutionary history of the Y chromosome