Bio-Based Polyhydroxyanthraquinones as High-Voltage Organic Electrode Materials for Batteries.

Organic materials have gained much attention as sustainable electrode materials for batteries. Especially bio-based organic electrode materials (OEMs) are very interesting due to their geographical independency and low environmental impact. However, bio-based OEMs for high-voltage batteries remain scarce. Therefore, in this work, a family of bio-based polyhydroxyanthraquinones (PHAQs)-namely 1,2,3,4,5,6,7,8-octahydroxyanthraquinone (OHAQ), 1,2,3,5,6,7-hexahydroxyanthraquinone (HHAQ), and 2,3,6,7-tetrahydroxyanthraquinone (THAQ)-and their redox polymers were synthesized. These PHAQs were synthesized from plant-based precursors and exhibit both a high-potential polyphenolic redox couple (3.5-4.0 V vs Li/Li+) and an anthraquinone redox moiety (2.2-2.8 V vs Li/Li+), while also showing initial charging capacities of up to 381 mAh g-1. To counteract the rapid fading caused by dissolution into the electrolyte, a facile polymerization method was established to synthesize PHAQ polymers. For this, the polymerization of HHAQ served as a model reaction where formaldehyde, glyoxal, and glutaraldehyde were tested as linkers. The resulting polymers were investigated as cathode materials in lithium metal batteries. PHAQ polymer composites synthesized using formaldehyde as linker and 10 wt % multiwalled carbon nanotubes (MWCNTs), namely poly(THAQ-formaldehyde)-10 wt % MWCNTs and poly(HHAQ-formaldehyde)-10 wt % MWCNTs, exhibited the best cycling performance in the lithium metal cells, displaying a high-voltage discharge starting at 4.0 V (vs Li/Li+) and retaining 81.6 and 77.3 mAh g-1, respectively, after 100 cycles.

Surface and Conductivity Characterization of Layered Organic Ionic Plastic Crystal (OIPC)-Polymer Films.

Organic ionic plastic crystals (OIPCs) are attractive solid electrolyte materials for advanced energy storage systems owing to their inherent advantages (e.g., high plasticity, thermal stability, and moderate ionic conductivity), which can be further improved/deteriorated by the addition of polymer or metal oxide nanoparticles. The role of the nanoparticle/OIPC combinations on the resultant interphase structure and transport properties, however, is still unclear due to the complexity within the composite structures. Herein, we demonstrate a systematic approach to specifically interrogating the interphase region by fabricating layered OIPC/polymer thin films via spin coating and correlating variation in the ionic conductivity of the OIPC with their microscopic structures. In-plane interdigitated electrodes have been employed to obtain electrochemical impedance spectroscopy (EIS) spectra on both OIPC and layered OIPC/polymer thin films. The thin-film EIS measurements were evaluated with conventional bulk EIS measurements on the OIPC pressed pellets and compared with EIS obtained from the OIPC-polymer composites. Interactions between the OIPC and polymer films as well as the morphology of the film surfaces have been characterized through multiple microscopic analysis tools, including scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic force microscopy, and optical profilometry. The combination of EIS analysis with the microscopic visualization of these unique layered OIPC/polymer thin films has confirmed the impact of the OIPC-polymer interphase region on the overall ionic conductivity of bulk OIPC-polymer composites. By changing the chemistry of the polymer substrate (i.e., PMMA, PVDF, and PVDF-HFP), the importance of compatibility between the components in the interphase region is clearly observed. The methods developed here can be used to screen and further understand the interactions among composite components for enhanced compatibility and conductivity.

Polyimides as Promising Cathodes for Metal-Organic Batteries: A Comparison between Divalent (Ca2+, Mg2+) and Monovalent (Li+, Na+) Cations.

Ca- and Mg-based batteries represent a more sustainable alternative to Li-ion batteries. However, multivalent cation technologies suffer from poor cation mass transport. In addition, the development of positive electrodes enabling reversible charge storage currently represents one of the major challenges. Organic positive electrodes, in addition to being the most sustainable and potentially low-cost candidates, compared with their inorganic counterparts, currently present the best electrochemical performances in Ca and Mg cells. Unfortunately, organic positive electrodes suffer from relatively low capacity retention upon cycling, the origin of which is not yet fully understood. Here, 1,4,5,8-naphthalenetetracarboxylic dianhydride-derived polyimide was tested in Li, Na, Mg, and Ca cells for the sake of comparison in terms of redox potential, gravimetric capacities, capacity retention, and rate capability. The redox mechanisms were also investigated by means of operando IR experiments, and a parameter affecting most figures of merit has been identified: the presence of contact ion-pairs in the electrolyte.

Dual redox-active porous polyimides as high performance and versatile electrode material for next-generation batteries.

Energy storage will be a primordial actor of the ecological transition initiated in the energy and transport sectors. As such, innovative approaches to design high-performance electrode materials are crucial for the development of the next generation of batteries. Herein, a novel dual redox-active and porous polyimide network (MTA-MPT), based on mellitic trianhydride (MTA) and 3,7-diamino-N-methylphenothiazine (MPT) monomers, is proposed for applications in both high energy density lithium batteries and symmetric all-organic batteries. The MTA-MPT porous polyimide was synthesized using a novel environmentally-friendly hydrothermal polymerization method. Rooted in its dual redox proprieties, the MTA-MPT porous polyimide exhibits a high theoretical capacity making it a very attractive cathode material for high energy density battery applications. The cycling performance of this novel electrode material was assessed in both high energy density lithium batteries and light-weight symmetric all-organic batteries, displaying excellent rate capability and long-term cycling stability.

Single-Ion Conducting Polymer Nanoparticles as Functional Fillers for Solid Electrolytes in Lithium Metal Batteries.

Composite solid electrolytes including inorganic nanoparticles or nanofibers which improve the performance of polymer electrolytes due to their superior mechanical, ionic conductivity, or lithium transference number are actively being researched for applications in lithium metal batteries. However, inorganic nanoparticles present limitations such as tedious surface functionalization and agglomeration issues and poor homogeneity at high concentrations in polymer matrixes. In this work, we report on polymer nanoparticles with a lithium sulfonamide surface functionality (LiPNP) for application as electrolytes in lithium metal batteries. The particles are prepared by semibatch emulsion polymerization, an easily up-scalable technique. LiPNPs are used to prepare two different families of particle-reinforced solid electrolytes. When mixed with poly(ethylene oxide) and lithium bis(trifluoromethane)sulfonimide (LiTFSI/PEO), the particles invoke a significant stiffening effect (E' > 106 Pa vs 105 Pa at 80 °C) while the membranes retain high ionic conductivity (σ = 6.6 × 10-4 S cm-1). Preliminary testing in LiFePO4 lithium metal cells showed promising performance of the PEO nanocomposite electrolytes. By mixing the particles with propylene carbonate without any additional salt, we obtain true single-ion conducting gel electrolytes, as the lithium sulfonamide surface functionalities are the only sources of lithium ions in the system. The gel electrolytes are mechanically robust (up to G' = 106 Pa) and show ionic conductivity up to 10-4 S cm-1. Finally, the PC nanocomposite electrolytes were tested in symmetrical lithium cells. Our findings suggest that all-polymer nanoparticles could represent a new building block material for solid-state lithium metal battery applications.

Macrophase-Separated Organic Ionic Plastic Crystals/PAMPS-Based Ionomer Electrolyte: A New Design Perspective for Flexible and Highly Conductive Solid-State Electrolytes.

A material design approach was taken for the preparation of an organic ionic plastic crystal (OIPC)-polymer electrolyte material that exhibited both good mechanical and transport properties. Previous attempts to form this type of electrolyte material resulted in the solvation of the OIPC by the ionomer and loss of the plastic crystal component. Here, we prepared, in situ, a macrophase-separated OIPC-polymer electrolyte system by adding lithium bis(fluorosulfonyl)imide (LiFSI) to a (PAMPS-N1222) ionomer. It was found that an optimal compositional window of 40-50 mol % LiFSI exists whereby the electrolyte conductivity suddenly increased 4 orders of magnitude while exhibiting elastic and flexible mechanical properties. The phase behavior and transport properties were studied using differential scanning calorimetry and 7Li and 19F solid-state nuclear magnetic resonance spectroscopy. This is the first example of a fabrication principle that lends itself to a wide range of promising OIPC and ionomeric materials. Subsequent studies are required to characterize and understand the morphology and conductive nature of these systems and their application as electrolyte materials.

Toward High-Energy-Density Lithium Metal Batteries: Opportunities and Challenges for Solid Organic Electrolytes.

With increasing demands for safe, high capacity energy storage to support personal electronics, newer devices such as unmanned aerial vehicles, as well as the commercialization of electric vehicles, current energy storage technologies are facing increased challenges. Although alternative batteries have been intensively investigated, lithium (Li) batteries are still recognized as the preferred energy storage solution for the consumer electronics markets and next generation automobiles. However, the commercialized Li batteries still have disadvantages, such as low capacities, potential safety issues, and unfavorable cycling life. Therefore, the design and development of electromaterials toward high-energy-density, long-life-span Li batteries with improved safety is a focus for researchers in the field of energy materials. Herein, recent advances in the development of novel organic electrolytes are summarized toward solid-state Li batteries with higher energy density and improved safety. On the basis of new insights into ionic conduction and design principles of organic-based solid-state electrolytes, specific strategies toward developing these electrolytes for Li metal anodes, high-energy-density cathode materials (e.g., high voltage materials), as well as the optimization of cathode formulations are outlined. Finally, prospects for next generation solid-state electrolytes are also proposed.

Innovative Electrolytes Based on Ionic Liquids and Polymers for Next-Generation Solid-State Batteries.

Electrolytes based on organic solvents used in current Li-ion batteries are not compatible with the next-generation energy storage technologies including those based on Li metal. Thus, there has been an increase in research activities investigating solid-state electrolytes, ionic liquids (ILs), polymers, and combinations of these. This Account will discuss some of the work from our teams in these areas. Similarly, other metal-based technologies including Na, Mg, Zn, and Al, for example, are being considered as alternatives to Li-based energy storage. However, the materials research required to effectively enable these alkali metal based energy storage applications is still in its relative infancy. Once again, electrolytes play a significant role in enabling these devices, and research has for the most part progressed along similar lines to that in advanced lithium technologies. Some of our recent contributions in these areas will also be discussed, along with our perspective on future directions in this field. For example, one approach has been to develop single-ion conductors, where the anion is tethered to the polymer backbone, and the dominant charge conductor is the lithium or sodium countercation. Typically, these present with low conductivity, whereas by using a copolymer approach or incorporating bulky quaternary ammonium co-cations, the effective charge separation is increased thus leading to higher conductivities and greater mobility of the alkali metal cation. This has been demonstrated both experimentally and via computer simulations. Further enhancements in ion transport may be possible in the future by designing and tethering more weakly associating anions to the polymer backbone. The second approach considers ion gels or composite polymer electrolytes where a polymerized ionic liquid is the matrix that provides both mechanical robustness and ion conducting pathways. The block copolymer approach is also demonstrated, in this case, to simultaneously provide mechanical properties and high ionic conductivity when used in combination with ionic-liquid electrolytes. The ultimate electrolyte material that will enable all high-performance solid-state batteries will have ion transport decoupled from the mechanical properties. While inorganic conductors can achieve this, their rigid, brittle nature creates difficulties. On the other hand, ionic polymers and their composites provide a rich area of chemistry to design and tune high ionic conductivity together with ideal mechanical properties.

Characterization of the phase behaviour of a novel polymerizable lyotropic ionic liquid crystal.

The development of new polymerizable lyotropic liquid crystals (LLCs) utilizing charged amphiphilic molecules such as those based on long chain imidazolium compounds, is a relatively new design direction for producing robust membranes with controllable nano-structures. Here we have developed a novel polymerizable ionic liquid based LLC, 1-hexadecyl-3-methylimidazolium acrylate (C16mimAcr), where the acrylate anion acts as the polymerizable moiety. The phase behaviour of the C16mimAcr upon the addition of water was characterized using small and wide angle X-ray scatterings, differential scanning calorimetry and polarized optical microscopy. We compare the phase behaviour of this new polymerizable LLC to that of the well known LLC chloride analogue, 1-hexadecyl-3-methylimidazolium chloride (C16mimCl). We find that the C16mimAcr system has a more complex phase behaviour compared to the C16mimCl system. Additional lyotropic liquid crystalline mesophases such as hexagonal phase (H1) and discontinuous cubic phase (I1) are observed at 20 °C for the acrylate system at 50 and 65 wt% water respectively. The appearance of the hexagonal phase (H1) and discontinuous cubic phase (I1) for the acrylate system is likely due to the strong hydrating nature of the acrylate anion, which increases the head group area. The formation of these additional mesophases seen for the acrylate system, especially the hexagonal phase (H1), coupled with the polymerization functionality offers great potential in the design of advanced membrane materials with selective and anisotropic transport properties.

A comparative review of measurement instruments to inform and evaluate effectiveness of disability inclusive development.

PURPOSE: A review of existing measurement instruments was conducted to examine their suitability to measure disability prevalence and assess quality of life, protection of disability rights and community participation by people with disabilities, specifically within the context of development programs in low and middle-income countries. METHODS: From a search of PubMed and the grey literature, potentially relevant measurement instruments were identified and examined for their content and psychometric properties, where possible. Criteria for inclusion were: based on the WHO's International Classification of Functioning Disability and Health (ICF), used quantitative methods, suitable for population-based studies of disability inclusive development in English and published after 1990. Characteristics of existing instruments were analysed according to components of the ICF and quality of life domains. RESULTS: Ten instruments were identified and reviewed according to the criteria listed above. Each version of instruments was analysed separately. Only three instruments included a component on quality of life. Domains from the ICF that were addressed by some but not all instruments included the environment, technology and communication. CONCLUSION: The measurement instruments reviewed covered the range of elements required to measure disability-inclusion within development contexts. However no single measurement instrument has the capacity to measure both disability prevalence and changes in quality of life according to contemporary disability paradigms. The review of measurement instruments supports the need for developing an instrument specifically intended to measure disability inclusive practice within development programs. Implications for Rehabilitation Surveys and tools are needed to plan disability inclusive development. Existing measurement tools to determine prevalence of disability, wellbeing, rights and access to the community were reviewed. No single validated tool exists for population-based studies, uses quantitative methods and the components of the ICF to measure prevalence of disability, well-being of people with disability and their access to their communities. A measurement tool that reflects the UNCRPD and addresses all components of the ICF is needed to assist in disability inclusive development, especially in low and mid resource countries.

[Promoting sexual and reproductive health as part of an educational program among Romani women]. / Education a la santé reproductive et sexuelle avec des femmes rom.

In 2012, the "Centre d'Accueil, de Soins et d'Orientation" run by Médecins du Monde in Bordeaux (France) developed an educational program aimed at promoting sexual and reproductive health among Romani women from Bulgaria and Romania. A preliminary study was conducted using a qualitative methodology involving focus groups and individual interviews. A close relationship was found between the participants' cultural beliefs about sexual and reproductive health and their precarious living conditions. An analytical framework focusing on representations of motherhood and birth control highlighted the resources and constraints shaping their attitudes and the challenges they face. The results provide support for a recent attempt to promote health among Romani women living in the area. More specifically, an educational approach designed to provide support and assistance was recently developed to help women find solutions tailored to their needs and designed to increase their decision-making abilities. The program also involves an advocacy approach. The implementation of the project is further supported by an assessment process, which will be followed by a summative evaluation of the resulting effects and an assessment of the impact of the program on the perception of reproductive health among the local Romani population.

Inducing alignment of cyclic peptide nanotubes through the use of structured ionic liquids.

We describe a convenient route to the alignment of cyclic peptide nanotubes (CPNs). The key lies in the use of nanostructured ionic liquids. An ionic liquid supported membrane with orientated domains is demonstrated, leading to aligned CPNs within a solid membrane.

A qualitative study on knowledge, perceptions, and attitudes of mothers and health care providers toward pneumococcal conjugate vaccine in Bandung, West Java, Indonesia.

UNLABELLED: Due to the high burden of pneumonia in Indonesia, the inclusion of pneumococcal conjugate vaccine (PCV) into Indonesia's National Immunization Program (NIP) is recommended by World Health Organization. Prior to the introduction of new vaccines, it is imperative to assess the perceptions of the public and medical community about the disease and the vaccine. The purpose of this qualitative study was to explore the knowledge, perceptions, and attitudes of mothers and health care providers (HCPs) toward PCV in Bandung, West Java, Indonesia. METHODOLOGY: Fifty-five respondents (26 mothers and 29 HCPs) were interviewed at public and private health care facilities in Bandung using semi-structured interviews in May-June 2011. Data were analyzed manually according to pre-defined themes. RESULTS: Although most mothers had low knowledge about PCV, did not perceive themselves as susceptible to the disease, perceived that cost was the main barrier to PCV access, and obtained little information on PCV, they considered pneumonia as a severe disease and a priority health problem, perceived benefits of the vaccine, and were likely to adopt it. Similarly, knowledge about PCV among most HCPs was limited. Despite perceiving cost as the main barrier, most HCPs perceived benefits of the vaccine, susceptibility and severity of the disease, regarded pneumonia as a priority health problem, and were likely to suggest the new vaccination. DISCUSSION/CONCLUSIONS: Despite the poor knowledge of mothers and HCPs about PCV, they are aware of the high burden of pneumonia and the need for a vaccine in the NIP. Perceived severity and benefits among mothers, and, additionally, perceived susceptibility among HCPs were manifested in the willingness to accept PCV. The findings would contribute to better understanding the factors, which could support decision-making about vaccine introduction, and be utilized for developing suitable messages for mothers and HCPs.

Near-vision impairment and unresolved vision problems in Indigenous Australian adults.

BACKGROUND: To describe near-vision impairment, self-reported unresolved vision problems and barriers to having near-vision correction in Indigenous Australians. DESIGN: A nationwide population-based study designed to determine the causes and prevalence of vision loss and utilization of eye care services. PARTICIPANTS: Indigenous Australians aged ≥40 years. METHODS: Using a multistage random cluster sampling methodology, 30 geographical areas stratified by remoteness were selected to obtain a representation of Indigenous Australians. Visual acuity was conducted using a standard E chart. A questionnaire collected data on eye health, eye care service utilization and vision-related quality of life. MAIN OUTCOME MEASURES: Near-vision impairment defined as presenting binocular near visual acuity

Applications of piezoelectric materials in oilfield services.

Piezoelectric materials are used in many applications in the oilfield services industry. Four illustrative examples are given in this paper: marine seismic survey, precision pressure measurement, sonic logging-while-drilling, and ultrasonic bore-hole imaging. In marine seismics, piezoelectric hydrophones are deployed on a massive scale in a relatively benign environment. Hence, unit cost and device reliability are major considerations. The remaining three applications take place downhole in a characteristically harsh environment with high temperature and high pressure among other factors. The number of piezoelectric devices involved is generally small but otherwise highly valued. The selection of piezoelectric materials is limited, and the devices have to be engineered to withstand the operating conditions. With the global demand for energy increasing in the foreseeable future, the search for hydrocarbon resources is reaching into deeper and hotter wells. There is, therefore, a continuing and pressing need for high-temperature and high-coupling piezoelectric materials.

Regenerated silk fibroin using protic ionic liquids solvents: towards an all-ionic-liquid process for producing silk with tunable properties.

We have shown that protic ionic liquids, pILs, are effective coagulation solvents for the regenerated of silk fibroin, RSF. We show that the choice of pIL has a dramatic effect on the composition of the RSF. Additionally the use of pILs as the coagulator eliminates the need for volatile organic solvents in silk processing.

Prevalence of self-reported diabetes and diabetic retinopathy in indigenous Australians: the National Indigenous Eye Health Survey.

BACKGROUND: To assess the prevalence of diabetes and diabetic retinopathy in indigenous Australians aged ≥40 years. DESIGN: The National Indigenous Eye Health Survey used a stratified, multistage cluster probability sampling frame to provide a representative sample of the indigenous Australian population. PARTICIPANTS: One thousand one hundred and eighty-nine eligible indigenous adults were examined using standardized procedures. METHODS: Each participant underwent a comprehensive eye examination included presenting and best corrected visual acuity, visual field, fundus and lens photography. MAIN OUTCOME MEASURES: Diabetic retinopathy. RESULTS: The prevalence of diabetes in the 1189 eligible indigenous adults was 37.3% (95% confidence interval: 34.6-40.2%). The prevalence of diabetic retinopathy among 394 people with diabetes was 29.7% (95% confidence interval: 25.2-34.2%), and 17.8% (95% confidence interval: 14.0-21.6%), 8.9% (95% confidence interval: 6.1-11.7%) and 3.1% (95% confidence interval: 1.3-4.7%) for mild or moderate diabetic retinopathy, clinically significant macular oedema and severe or proliferative diabetic retinopathy, respectively. Diabetic retinopathy was presented in 6.3% in those who did not report diabetes. The risk of diabetic retinopathy increased with duration of diabetes (the adjusted odds ratios were 3.4 for 10-19 years, 6.1 for 20-29 years and 25.8 for ≥30 years). CONCLUSIONS: The prevalence of self-reported diabetes in indigenous Australians is more than eight times higher than that in non-indigenous Australians. The prevalence of diabetic retinopathy in people with diabetes is similar to that of non-indigenous Australians.

Self-reported vision and health of indigenous Australians.

PURPOSE: To describe the self-reported vision, history of eye disease and general health of indigenous Australian participants in the National Indigenous Eye Health Survey. METHODS: Using a multistage cluster sampling methodology, 30 geographic areas, stratified by remoteness, were selected to provide a representative population of indigenous Australians aged 5-15 years and 40 years and over. Before an eye examination, participants completed a questionnaire about their eye health and eye care facilities consulted, satisfaction with their vision and general health. RESULTS: A total of 1694 indigenous children (49.2% female, mean age 9.5 ± 2.9 years) and 1189 adults (61.0% female, mean age 53.1 ± 9.7 years) participated. Three-quarters of adults (259/342) and 88.4% of children (129/146) wore the right distance glasses. Adults from remote areas were less likely to have refractive error (P = 0.002) as well as males versus females (P = 0.02). Similar results were found for children. Adults wearing appropriate distance glasses were as satisfied with their vision as people with normal vision who did not need glasses (P = 0.6). Both groups were more satisfied with their distance vision than people with poor presenting vision (P = 0.007). Self-report of cataract, diabetic retinopathy, glaucoma and age-related macular degeneration did not match with clinical findings (P < 0.001). Over 37% of adults (417/1187) and 1.3% of children (22/1691) reported having diabetes. CONCLUSION: The National Indigenous Eye Health Survey provided information to guide future planning of eye health prevention strategies for indigenous Australians. Findings indicate the importance of correcting refractive error to improve quality of life. Prevention messages should be renewed in appropriate sociocultural formats.

Cataract in indigenous Australians: the National Indigenous Eye Health Survey.

BACKGROUND: To determine the prevalence of vision loss due to cataract in indigenous Australians. METHODS: A national, stratified, random cluster sample was selected in 30 communities across Australia. Data collection was undertaken in 2008. Adults 40 years and older were examined using a standardized protocol that included a questionnaire. The presence of visually significant cataract was assessed. RESULTS: Response rates were good and 1189 indigenous adults were examined and overall recruitment was 72%. Low vision (<6/12-6/60) due to cataract occurred in 2.52% (1.63-3.41%) and blindness (<6/60) in 0.59% (95% CI: 0.24-1.21%). The cataract coverage rate (proportion of those with visually significant cataract who had been operated on) was 65.3% (95% CI: 55.0-74.6%). Projections suggest that there are 3234 indigenous adults with vision loss from cataract. CONCLUSIONS: Cataract remains a major cause of vision loss in Aboriginal and Torres Strait Islander peoples. There were no significant regional or state differences in the prevalence of cataract or of cataract surgical coverage, which suggests that increased cataract surgery services are required across the country to address cataract in indigenous Australians.