Electrodeposited Cu2Sb as anode material for 3-dimensional Li-ion microbatteries

An increasing demand on high energy and power systems has arisen not only with the development of electric vehicle (EV), hybrid electric vehicle (HEV), telecom, and mobile technologies, but also for specific applications such as powering of microelectronic systems. To power those microdevices, an extra variable is added to the equation: a limited footprint area. Three-dimensional (3D) microbatteries are a solution to combine high-density energy and power. In this work, we present the formation of Cu2Sb onto three-dimensionally architectured arrays of Cu current collectors. Sb electrodeposition conditions and annealing post treatment are discussed in light of their influence on the morphology and battery performances. An increase of cycling stability was observed when Sb was fully alloyed with the Cu current collector. A subsequent separator layer was added to the 3D electrode when optimized. Equivalent capacity values are measured for at least 20 cycles. Work is currently devoted to the identification of the causes of capacity fading

Electrochemical Method for Direct Deposition of Nanometric Bismuth and Its Electrochemical Properties vs Li

We report that nanometric bismuth can directly be electrodeposited at room temperature without the use of a nanoporous template. The morphology, microstructure, and purity of the as-prepared electrodeposits were characterized by scanning electron microscopy, transmission electron microscopy, and infrared spectroscopy. Typically, well-crystallized nanometer-sized particles of Bi ranging from 10 to 20 nm are obtained. The key to success of such a process lies in the electrochemical coreduction of pyrocatechol violet during the bismuth deposition, which disturbs the electrocrystallization process. As a first possible application, we show that Bi/Cu nanoarchitectured electrodes exhibit interesting rate capabilities when used as electrode material vs Li

Experimental and theoretical studies of tetramethoxy-p-benzoquinone: infrared spectra, structural and lithium insertion properties

International audienceIn the search for low-polluting electrode materials for batteries, the use of redox-active organic compounds represents a promising alternative to conventional metal-based systems. In this article we report a combined experimental and theoretical study of tetramethoxy-p-benzoquinone (TMQ). In carbonate-based electrolytes, electrochemical behaviour of this compound is characterized by a reversible insertion process located at approximately 2.85 V vs. Li+/Li0. This relatively high potential reactivity, coupled with our effort to develop computational methodologies in the field of organic electrode materials, prompted us to complement these experimental data with theoretical studies performed using density functional theory (DFT). Single crystals of TMQ were synthesized and thoroughly characterized showing that this quinonic species crystallised in the P21/n space group. The experimental crystal structure of TMQ was then used to assess various DFT methods. The structural features and vibrational spectra were thus predicted by using as a whole five common density functionals (PBE, LDA, revPBE, PBEsol, B3PW91) with and without a semi-empirical correction to account for the van der Waals interactions using either Grimme's (DFT-D2) or Tkatchenko-Scheffler (TS) scheme. The most reliable combination of the DFT functional and the explicit dispersion correction was chosen to study the Li-intercalated molecular crystal (LiTMQ) with the view of indentifying Li insertion sites. A very close agreement with the experiment was found for the average voltage by using the most stable relaxed hypothetical LiTMQ structure. Additionally, a comparison of vibrational spectra gained either for TMQ molecule and its dimer in gas phase or through periodic calculation was undertaken with respect to the experimentally measured infrared spectra. The topological features of the bonds were also investigated in conjunction with estimates of net atomic charges to gain insight into the effect of chemical bonding and intermolecular interaction on Li intercalation. Finally, π-electron delocalization of both quinone and alkali salts of p-semiquinone were determined using the Harmonic Oscillator model of Aromaticity (HOMA) or aromatic fluctuation index (FLU) calculations

Week 96 efficacy and safety results of the phase 3, randomized EMERALD trial to evaluate switching from boosted-protease inhibitors plus emtricitabine/tenofovir disoproxil fumarate regimens to the once daily, single-tablet regimen of darunavir/cobicistat/emtricitabine/tenofovir alafenamide (D/C/F/TAF) in treatment-experienced, virologically-suppressed adults living with HIV-1

Darunavir/cobicistat/emtricitabine/tenofovir alafenamide (D/C/F/TAF) 800/150/200/10 mg was investigated through 96 weeks in EMERALD (NCT02269917). Virologically-suppressed, HIV-1-positive treatment-experienced adults (previous non-darunavir virologic failure [VF] allowed) were randomized (2:1) to D/C/F/TAF or boosted protease inhibitor (PI) plus emtricitabine/tenofovir-disoproxil-fumarate (F/TDF) over 48 weeks. At week 52 participants in the boosted PI arm were offered switch to D/C/F/TAF (late-switch, 44 weeks D/C/F/TAF exposure). All participants were followed on D/C/F/TAF until week 96. Efficacy endpoints were percentage cumulative protocol-defined virologic rebound (PDVR; confirmed viral load [VL] >= 50 copies/mL) and VL = 50 copies/mL (VF) (FDA-snapshot analysis). Of 1141 randomized patients, 1080 continued in the extension phase. Few patients had PDVR (D/C/F/TAF: 3.1%, 24/763 cumulative through week 96; late-switch: 2.3%, 8/352 week 52-96). Week 96 virologic suppression was 90.7% (692/763) (D/C/F/TAF) and 93.8% (330/352) (late-switch). VF was 1.2% and 1.7%, respectively. No darunavir, primary PI, tenofovir or emtricitabine resistance-associated mutations were observed post-baseline. No patients discontinued for efficacy-related reasons. Few discontinued due to adverse events (2% D/C/F/TAF arm). Improved renal and bone parameters were maintained in the D/C/F/TAF arm and observed in the late-switch arm, with small increases in total cholesterol/high-density-lipoprotein-cholesterol ratio. A study limitation was the lack of a control arm in the week 96 analysis. Through 96 weeks, D/C/F/TAF resulted in low PDVR rates, high virologic suppression rates, very few VFs, and no resistance development. Late-switch results were consistent with D/C/F/TAF week 48 results. EMERALD week 96 results confirm the efficacy, high genetic barrier to resistance and safety benefits of D/C/F/TAF

Primary liver cancer is more aggressive in HIV-HCV coinfection than in HCV infection. A prospective study (ANRS CO13 Hepavih and CO12 Cirvir)

OBJECTIVE: Since HAART, primary liver cancer has emerged as an increasing cause of morbidity and mortality in patients with HIV infection. Our aim was to compare characteristics and outcome of primary liver cancer according to HIV status in HCV cirrhotic patients submitted to periodic ultrasonographic surveillance. METHODS: All patients with primary liver cancer and cirrhosis were selected from two prospective cohorts (ANRS CO12 Cirvir, viral cirrhosis, n=1081; ANRS CO13 Hepavih, HIV-HCV coinfection, n=1175). Cirrhosis was diagnosed by liver biopsy in monoHCV group and biopsy and/or non-invasive tests in HIV-HCV group. Ultrasonographic surveillance was performed every 6 months. Diagnosis of primary liver cancer was established according to EASL-AASLD guidelines. RESULTS: Primary liver cancer was diagnosed in 32 patients, 16 in each group, and corresponded to hepatocellular carcinoma in all except for two cholangiocarcinomas in HIV-HCV patients. Ultrasonographic follow-up was similar (median time since last ultrasonographic without focal lesion: 237 days in HIV-HCV group (n=12) versus 208 days in HCV group, NS). At primary liver cancer diagnosis HIV-HCV patients were markedly younger (48 vs. 60 yrs, P<0.001), primary liver cancer was more advanced in HIV-HCV patients (single nodule: 43% vs. 75%, P=0.07; mean diameter of main nodule: 24 vs. 16 mm, P=0.006; portal obstruction: 3 vs. 0). Curative treatment was performed in four HIV-HCV patients versus 11 HCV patients (P=0.017). During follow-up, 10 HIV-HCV patients died versus only one HCV patient (P=0.0005). CONCLUSIONS: This result suggests more aggressiveness for tumors in HIV infected patients and, if confirmed, could result in shortening the length between ultrasonographic examinations

Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting

Developing earth-abundant, active and stable electrocatalysts which operate in the same electrolyte for water splitting, including oxygen evolution reaction and hydrogen evolution reaction, is important for many renewable energy conversion processes. Here we demonstrate the improvement of catalytic activity when transition metal oxide (iron, cobalt, nickel oxides and their mixed oxides) nanoparticles (~20 nm) are electrochemically transformed into ultra-small diameter (2–5 nm) nanoparticles through lithium-induced conversion reactions. Different from most traditional chemical syntheses, this method maintains excellent electrical interconnection among nanoparticles and results in large surface areas and many catalytically active sites. We demonstrate that lithium-induced ultra-small NiFeOx nanoparticles are active bifunctional catalysts exhibiting high activity and stability for overall water splitting in base. We achieve 10 mA cm−2 water-splitting current at only 1.51 V for over 200 h without degradation in a two-electrode configuration and 1 M KOH, better than the combination of iridium and platinum as benchmark catalysts.open10

A log-normal spectral analysis of inorganic grain-size distributions from a Canadian boreal lake core: Towards refining depositional process proxy data from high latitude lakes

Better methods for interpreting grain size spectra will enhance current understanding of past transport–depositional processes. A high-resolution inorganic grain-size dataset has been measured from a freeze core extracted from ‘Alberta Lake E’ a boreal fresh water lake 40 km east of the Athabasca Oil Sands in north-eastern Alberta, Canada. The grain-size spectra are remarkably consistent throughout the core, exhibiting a structure comprising six persistent grain-size distributions below ca 250 μm, plus a rare medium-sand distribution. Automated deconvolution of the grain-size spectra produced poor results. Constraining the modes of two of the distributions produced deconvolution solutions that were statistically excellent and consistent with the structure of each spectrum. Statistical analysis of the ‘constrained’ solutions indicates that deconvolution successfully extracted independent grain-size populations. Conversely, the multimodal spectra generate traditional measures (for example, mean grain size) that are inconsistent combinations of different individual populations, and thus are poor proxies of transport–depositional processes. Alberta Lake E is situated in a boreal wetland landscape where sediment delivery is dominated by overland flow transport during spring melt. This context means that the Alberta Lake E grain-size spectra can be interpreted to reflect: (i) a bedload component transported during short-duration high discharge events that reflect the intensity of the melt; and (ii) a finer suspended load component representing material whose magnitude is controlled by the volume of the spring melt. Stratigraphically, bedload and suspended load populations demonstrate different short-wavelength and long-wavelength cyclicity, suggesting that spring melt is likely to be driven by cyclic external forcing factors. The links between the grain-size spectra and spring melt have potential for generating proxy records that better capture the external controls over spring melt in boreal systems, and the risks associated with these energetic hydrodynamics. This is exemplified by the coarsest Alberta Lake E distributions, which indicate that more intense spring melt dynamics occurred in pre-historical times

2D film of carbon nanofibers elastically astricted MnO microparticles: A flexible binder-free anode for highly reversible lithium ion storage

MnO as anode materials has received particular interest owing to its high specific capacity, abundant resources and low cost. However, it is still a serious problem that large volume change (>170%) during the lithiation/delithiation processes results in poor rate capability and fast capacity decay. With homogenous crystals of MnO grown in the network of carbon nanofibers(CNF)，binding effect of CNFs can effectively weaken the volume change of MnO during cycles. In this work, CNF/MnO flexible electrode for lithium-ion batteries is designed and synthesized. The carbon nanofibers play the roles of conductive channel and elastically astricting MnO particles during lithiation/delithiation. CNF/MnO as binder-free anode delivers specific capacity of 983.8 mAh g−1 after 100th cycle at a current density of 0.2 A g−1, and 600 mAh g−1 at 1 A g−1 which are much better than those of pure MnO and pure CNF. The ex-situ FESEM images of CNF/MnO clearly show the relative volume change of MnO/CNF as anode under various discharging and charging time. CNFs can elastically buffer the volume change of MnO during charging/discharging cycles. This work presents a facile and scalable approach for synthesizing a novel flexible binder-free anode of CNF/MnO for potential application in highly reversible lithium storage devices

3D hierarchical porous graphene aerogel with tunable meso-pores on graphene nanosheets for high-performance energy storage

New and novel 3D hierarchical porous graphene aerogels (HPGA) with uniform and tunable meso-pores (e.g., 21 and 53 nm) on graphene nanosheets (GNS) were prepared by a hydrothermal self-assembly process and an in-situ carbothermal reaction. The size and distribution of the meso-pores on the individual GNS were uniform and could be tuned by controlling the sizes of the Co3O4 NPs used in the hydrothermal reaction. This unique architecture of HPGA prevents the stacking of GNS and promises more electrochemically active sites that enhance the electrochemical storage level significantly. HPGA, as a lithium-ion battery anode, exhibited superior electrochemical performance, including a high reversible specific capacity of 1100 mAh/g at a current density of 0.1 A/g, outstanding cycling stability and excellent rate performance. Even at a large current density of 20 A/g, the reversible capacity was retained at 300 mAh/g, which is larger than that of most porous carbon-based anodes reported, suggesting it to be a promising candidate for energy storage. The proposed 3D HPGA is expected to provide an important platform that can promote the development of 3D topological porous systems in a range of energy storage and generation fields

Fungal nanoscale metal carbonates and production of electrochemical materials

Fungal biomineralization of carbonates results in metal removal from solution or immobilization within a solid matrix. Such a system provides a promising method for removal of toxic or valuable metals from solution, such as Co, Ni, and La, with some carbonates being of nanoscale dimensions. A fungal Mn carbonate biomineralization process can be applied for the synthesis of novel electrochemical materials.</p