Hexavalent Ions Insertion in Garnet Li7 La3 Zr2 O12 Toward a Low Temperature Densification Reaction.

Nowadays, solid electrolytes are considered the main alternative to conventional liquid electrolytes in lithium batteries. The fabrication of these materials is however limited by the strict synthesis conditions, requiring high temperatures which can negatively impact the final performances. Here, it is shown that a modification of garnet-based Li7 La3 Zr2 O12 (LLZO) and the incorporation of tellurium can accelerate the synthesis process by lowering the formation temperature of cubic LLZO at temperatures below 700 °C. Optimized synthesis at 750 °C showed a decrease in particle size and cell parameter for samples with higher amounts of Te and the evaluation of electrochemical performances reported for LLZO Te0.25 a value of ionic conductivity of 5,15×10-5  S cm-1 after hot-pressing at 700 °C, two orders of magnitude higher than commercial Al-LLZO undergoing the same working conditions, and the highest value at this densification temperature. Partial segregation of Te-rich phases occurs for high-temperature densification. Our study shows the advantages of Te insertion on the sintering process of LLZO garnet and demonstrates the achievement of highly conductive LLZO with a low-temperature treatment.

Achieving High Stability and Performance in P2-Type Mn-Based Layered Oxides with Tetravalent Cations for Sodium-Ion Batteries.

P2-type sodium-manganese-based layered cathodes, owing to their high capacity from both cationic and anionic redox, are a potential candidate for Na-ion batteries (NIBs) to replace Li-ion technology in certain applications. Still, the structure instability originating from irreversible oxygen redox at high voltage remains a challenge. Here, a high sustainability cobalt-free P2-Na0.72 Mn0.75 Li0.24 X0.01 O2  (X = Ti/Si) cathode is developed. The outstanding capacity retention and voltage retention after 150 cycles are obtained in half-cells. The finding shows that Ti localizes on the surface while Si diffuses to the bulk of the particles. Thus, Ti can act as a protective layer that alleviates side reactions in carbonate-based electrolyte. Meanwhile, Si can regulate the local electronic structure and suppress oxygen redox activities. Notably, full-cells with hard carbon (≈300-335 W h kg-1 based on the cathode mass) deliver the capacity retention of 83% for P2-Na0.72 Mn0.75 Li0.24 Si0.01 O2  and 66% for P2-Na0.72 Mn0.75 Li0.24 Ti0.01 O2  after 500 cycles; this electrochemical stability is the best compared to other reported cathodes based on oxygen redox at present. The superior cycle performance also stems from the ability to inhibit microcracking and planar gliding within the particles. Altogether, this finding offers a new composition for developing high-performance low-cost cathodes for NIBs and highlights the unique role of Ti/Si ions.

Unveiling the Cation Exchange Reaction between the NASICON Li1.5Al0.5Ge1.5(PO4)3 Solid Electrolyte and the pyr13TFSI Ionic Liquid.

Recently, the formation of the ceramic-ionic liquid composite has attracted huge interest in the scientific community. In this work, we investigated the chemical reactions occurring between NASICON LAGP ceramic electrolyte and ionic liquid pyr13TFSI. This study allowed us to identify the cation exchange reaction pyr13-Li occurring on the LAGP surface, forming a LiTFSI salt that was detected by the nuclear magnetic resonance analysis. In addition, using 6Li foils, we succeeded in demonstrating that both LAGP and LiTFSI:pyr13TFSI participate in the diffusion of Li ions by the formation of an ionic bridge between two species.

Pillar-beam structures prevent layered cathode materials from destructive phase transitions.

Energy storage with high energy density and low cost has been the subject of a decades-long pursuit. Sodium-ion batteries are well expected because they utilize abundant resources. However, the lack of competent cathodes with both large capacities and long cycle lives prevents the commercialization of sodium-ion batteries. Conventional cathodes with hexagonal-P2-type structures suffer from structural degradations when the sodium content falls below 33%, or when the integral anions participate in gas evolution reactions. Here, we show a "pillar-beam" structure for sodium-ion battery cathodes where a few inert potassium ions uphold the layer-structured framework, while the working sodium ions could diffuse freely. The thus-created unorthodox orthogonal-P2 K0.4[Ni0.2Mn0.8]O2 cathode delivers a capacity of 194 mAh/g at 0.1 C, a rate capacity of 84% at 1 C, and an 86% capacity retention after 500 cycles at 1 C. The addition of the potassium ions boosts simultaneously the energy density and the cycle life.

High Capacity and High Efficiency Maple Tree-Biomass-Derived Hard Carbon as an Anode Material for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are in the spotlight because of their potential use in large-scale energy storage devices due to the abundance and low cost of sodium-based materials. There are many SIB cathode materials under investigation but only a few candidate materials such as carbon, oxides and alloys were proposed as anodes. Among these anode materials, hard carbon shows promising performances with low operating potential and relatively high specific capacity. Unfortunately, its low initial coulombic efficiency and high cost limit its commercial applications. In this study, low-cost maple tree-biomass-derived hard carbon is tested as the anode for sodium-ion batteries. The capacity of hard carbon prepared at 1400 °C (HC-1400) reaches 337 mAh/g at 0.1 C. The initial coulombic efficiency is up to 88.03% in Sodium trifluoromethanesulfonimide (NaTFSI)/Ethylene carbonate (EC): Diethyl carbonate (DEC) electrolyte. The capacity was maintained at 92.3% after 100 cycles at 0.5 C rates. The in situ X-ray diffraction (XRD) analysis showed that no peak shift occurred during charge/discharge, supporting a finding of no sodium ion intercalates in the nano-graphite layer. Its low cost, high capacity and high coulombic efficiency indicate that hard carbon is a promising anode material for sodium-ion batteries.

High-Capacity and Long-Cycle Life Aqueous Rechargeable Lithium-Ion Battery with the FePO4 Anode.

Aqueous lithium-ion batteries are emerging as strong candidates for a great variety of energy storage applications because of their low cost, high-rate capability, and high safety. Exciting progress has been made in the search for anode materials with high capacity, low toxicity, and high conductivity; yet, most of the anode materials, because of their low equilibrium voltages, facilitate hydrogen evolution. Here, we show the application of olivine FePO4 and amorphous FePO4·2H2O as anode materials for aqueous lithium-ion batteries. Their capacities reached 163 and 82 mA h/g at a current rate of 0.2 C, respectively. The full cell with an amorphous FePO4·2H2O anode maintained 92% capacity after 500 cycles at a current rate of 0.2 C. The acidic aqueous electrolyte in the full cells prevented cathodic oxygen evolution, while the higher equilibrium voltage of FePO4 avoided hydrogen evolution as well, making them highly stable. A combination of in situ X-ray diffraction analyses and computational studies revealed that olivine FePO4 still has the biphase reaction in the aqueous electrolyte and that the intercalation pathways in FePO4·2H2O form a 2-D mesh. The low cost, high safety, and outstanding electrochemical performance make the full cells with olivine or amorphous hydrated FePO4 anodes commercially viable configurations for aqueous lithium-ion batteries.

Measuring Spatially Resolved Collective Ionic Transport on Lithium Battery Cathodes Using Atomic Force Microscopy.

One of the main challenges in improving fast charging lithium-ion batteries is the development of suitable active materials for cathodes and anodes. Many materials suffer from unacceptable structural changes under high currents and/or low intrinsic conductivities. Experimental measurements are required to optimize these properties, but few techniques are able to spatially resolve ionic transport properties at small length scales. Here we demonstrate an atomic force microscope (AFM)-based technique to measure local ionic transport on LiFePO4 to correlate with the structural and compositional analysis of the same region. By comparing the measured values with density functional theory (DFT) calculations, we demonstrate that Coulomb interactions between ions give rise to a collective activation energy for ionic transport that is dominated by large phase boundary hopping barriers. We successfully measure both the collective activation energy and the smaller single-ion bulk hopping barrier and obtain excellent agreement with values obtained from our DFT calculations.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries.

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2).

Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.

Emergence of Metallic Properties at LiFePO4 Surfaces and LiFePO4/Li2S Interfaces: An Ab Initio Study.

The atomic and electronic structures of the LiFePO4 (LFP) surface, both bare and reconstructed upon possible oxygenation, are theoretically studied by ab initio methods. On the basis of total energy calculations, the atomic structure of the oxygenated surface is proposed, and the effect of surface reconstruction on the electronic properties of the surface is clarified. While bare LFP(010) surface is insulating, adsorption of oxygen leads to the emergence of semimetallic behavior by inducing the conducting states in the band gap of the system. The physical origin of these conducting states is investigated. We further demonstrate that deposition of Li2S layers on top of oxygenated LFP(010) surface leads to the formation of additional conducting hole states in the first layer of Li2S surface because of the charge transfer from sulfur p-states to the gap states of LFP surface. This demonstrates that oxygenated LFP surface not only provides conducting layers itself, but also induces conducting channels in the top layer of Li2S. These results help to achieve further understanding of potential role of LFP particles in improving the performance of Li-S batteries through emergent interface conductivity.

Nicardipine in the treatment of aneurysmal subarachnoid haemorrhage: a meta-analysis of published data.

Nicardipine is a dihydropyridine-type Ca(2+) channel blocker with a powerful antihypertensive activity and a unique cerebrovascular profile. Recent studies have examined nicardipine for the treatment of patients with aneurysmal subarachnoid haemorrhage (SAH), but have shown inconsistent results. In the current study, a meta-analysis was performed to assess the clinical effectiveness of nicardipine in the prevention of cerebral vasospasm in patients who had suffered from aneurysmal SAH. Medline, EMBASE, and PubMed databases were searched for the controlled trials evaluating nicardipine for treating SAH after a ruptured aneurysm, without language restrictions. Moreover, a manual search of the bibliographies of relevant articles was also conducted. Two researchers of the present study independently performed the literature search and the data extraction. The meta-analyses were performed using the software RevMan 4.2.10 (provided by the Cochrane Collaboration, Oxford, UK). Five published manuscripts involving 1,154 patients were included in this meta-analysis. Nicardipine infusion reduced the risk of poor outcome (death, vegetative state, or dependency) and mortality, with an odds ratio (OR) of 0.58 [95 % confidence interval (CI) 0.37-0.90] and 0.45 (95 % CI 0.15-1.29), respectively. This meta-analysis suggests that nicardipine therapy reduces the likelihood of poor outcome and mortality in patients after aneurysmal SAH.

SymGF: a symbolic tool for quantum transport analysis and its application to a double quantum dot system.

We report the development and an application of a symbolic tool, called SymGF, for analytical derivations of quantum transport properties using the Keldysh nonequilibrium Green's function (NEGF) formalism. The inputs to SymGF are the device Hamiltonian in the second quantized form, the commutation relation of the operators and the truncation rules of the correlators. The outputs of SymGF are the desired NEGF that appear in the transport formula, in terms of the unperturbed Green's function of the device scattering region and its coupling to the device electrodes. For complicated transport analysis involving strong interactions and correlations, SymGF provides significant assistance in analytical derivations. Using this tool, we investigate coherent quantum transport in a double quantum dot system where strong on-site interaction exists in the side-coupled quantum dot. Results obtained by the higher-order approximation and Hartree-Fock approximation are compared. The higher-order approximation reveals Kondo resonance features in the density of states and conductances. Results are compared both qualitatively and quantitatively to the experimental data reported in the literature.