Lithium storage in disordered graphitic materials: a semi-quantitative study of the relationship between structure disordering and capacity.

The application of the graphitic anode is restricted by its low theoretical specific capacity of 372 mA h g(-1). Higher capacity can be achieved in the graphitic anode by modifying its structure, but the detailed storage mechanism is still not clear. In this work, the mechanism of the lithium storage in a disordered graphitic structure has been systematically studied. It is found that the enhanced capacity of the distorted graphitic structure does not come from lithium-intercalation, but through a capacitive process, which depends on the disordering degree and the porous structure.

Carbon coated Na7Fe7(PO4)6F3: A novel intercalation cathode for sodium-ion batteries

Electrode materials are being developed to realise sodium-ion batteries that can provide energy storage solutions. Here, we develop amorphous carbon coated Na₇Fe₇(PO₄)₆F₃, prepared by combining hydrothermal and solid state reaction methods, as an insertion electrode for sodium-ion batteries applications. Na₇Fe₇(PO₄)₆F₃ particles are surrounded by a thin layer (∼1.5–2 nm) of amorphous carbon. The Na₇Fe₇(PO₄)₆F₃/C composite cathode undergoes reversible sodium intercalation/de-intercalation with an average operational potential of ∼3.0 V (vs Na⁺/Na). This cathode has a capacity of 65 mA h g⁻¹ at 100 mA g⁻¹ current after 60 cycles and features twice higher capacity than that of an uncoated Na₇Fe₇(PO₄)₆F₃ sample. Therefore, the carbon-coated Na₇Fe₇(PO₄)₆F₃ composite presents feasible sodium intercalation/de-intercalation capacity, offering possibilities for developing a low cost, high performance sodium-ion battery positive electrode.

Effect of different carbon-coating ways on the microstructure and electrochemical performance of LiFePO4/C cathodes

Through comparative studying on LiFePO4/C preparation process of adding carbon source in precursor and pre-sintered material, marked as LFP-1 (in-situ carbon coating) and LFP-2 respectively, by means of C-S test, XRD, SEM, BET, Raman, the effects of carbon content, morphology, particle size and surface carbon structure on the electrochemical performance of LiFePO4/C cathodes were investigated. SEM images showed that particle sizes of LFP-1 and LFP-2 are about 10μm and 100nm respectively. The EIS and galvnostatic charge-discharge tests indicated that LFP-1 has lower charge transfer resistance (Rct), better rate and cycle performance than that of LFP-2, which can be attributed to the different microstructure and the higher degree of graphitized carbon of LiFePO4/C. Raman spectroscopic analysis showed that the ratio of the ID/IG and Asp3/Asp2 of LFP-1 is lower that of LFP-2, which means the degree of graphitized carbon of LFP-1 is higher than that of LEP-2. These results have important significance for improving the overall performance of olivine cathode materials for lithium ion batteries.

Electrochemical performance of LiFe1-xMnxPO4/C materials prepared by ball milling

LiFe1-xMnxPO4/C composite materials as cathode materials in Li-ion batteries have been synthesised and their electrochemical properties have been investigated. The samples were synthesised by using high energy ball milling of commercially available precursors (Li2C2O4, FeC2O4.2H2O, MnC2O4.2H2O, NH4H2PO4) and then heated at 600°C. The morphology and structure of the heated samples were analysed by means of SEM and X-ray diffraction. The olivine structure of the LiFe1-xMnxPO4/C composite was obtained. A slight shift of the peaks to smaller 2θ angles with the increasing Mn/Fe ratios is observed due to the increase in lattice parameters. The influence of different Mn/Fe ratios on electrical and electrochemical performances were studied by charge-discharge and cyclic voltammetry (CV) testing. The CV curves of the pure LiFePO4 and LiMnPO4 show the expected Fe2+/Fe3+ peak around 3·5 V and Mn2+/Mn3+ peak around 4·1 V, respectively. The addition of manganese increases the discharge voltage from 3·5 to 4·1 V.

Lamotrigine compared with lithium in mania: a double-blind randomized controlled trial.

Preliminary data from case reports and small open trials suggest a role for lamotrigine in the treatment of bipolar disorder, although controlled data for the manic phase are lacking.

Olanzapine compared to lithium in mania: a double-blind randomized controlled trial.

Neuroleptics are of established efficacy in mania. Controlled data on the use of olanzapine in mania is however, absent. In this study, 30 patients meeting DSM-IV criteria for mania were randomly allocated to receive either olanzapine or lithium in a 4 week double-blind randomized controlled design. There were no significant outcome differences between the two groups on any of the primary outcome measures, the Brief Psychiatric Rating Scale (lithium 28.2; olanzapine 28.0; P = 0.44); Clinical Global Impression (CGI) improvement scale (lithium 2.75, olanzapine 2.36; P = 0.163) or the Mania Scale (lithium 13.2, olanzapine 10.2; P = 0.315). Olanzapine was however, significantly superior to lithium on the CGI-severity scale at week 4 (lithium 2.83, olanzapine 2.29; P = 0.025). Olanzapine did not differ from lithium in terms of treatment emergent extrapyramidal side-effects as measured by the Simpson-Angus Scale. Olanzapine appears to be at least as effective as lithium in the treatment of mania.

Lithium blocks 45Ca2+ uptake into platelets in bipolar affective disorder and controls.

The basal uptake of radiolabelled 45Ca2+ into platelets and the effect of 1 mM lithium on uptake was measured in manic (n = 13) and depressed (n = 15) patients with bipolar disorder and in controls (n = 13). Lithium was significantly associated with inhibition of uptake of 45Ca2+ into platelets in all three groups. There were no significant intergroup differences in either basal levels of calcium uptake or the effects of lithium on calcium uptake (analysis of variance).

Risperidone compared with both lithium and haloperidol in mania: a double-blind randomized controlled trial.

Case reports and studies of other neuroleptics suggest the efficacy of risperidone in the treatment of mania. Forty-five inpatients with DSM-IV mania were studied in a 28-day randomized, controlled, double-blind trial of either 6 mg daily of risperidone, 10 mg daily of haloperidol, or 800 to 1200 mg daily of lithium. The patients in all three groups showed a similar improvement on the total score for all rating scales at day 28 (Brief Psychiatric rating scale; lithium 9.1, haloperidol 4.9, risperidone 6.5, F = 1.01, df = 2, p = 0.37; Mania rating scale; lithium 15.7, haloperidol 10.2, risperidone 12.4, F = 1.07, df = 2, p = 0.35 [analysis of variance]). The Global Assessment of Functioning and Clinical Global Impression data showed a similar pattern of improvement. This study suggests that risperidone is of equivalent efficacy to lithium and haloperidol in the management of acute mania. The extrapyramidal side effects of risperidone and haloperidol were not significantly different.

Superiority of lithium over verapamil in mania: a randomized, controlled, single-blind trial.

Both case reports and small controlled studies suggest the efficacy of verapamil in the treatment of mania.

Supplementing cold plasma with heat enables doping and nano-structuring of metal oxides

Nitrogen doped SnO2 polycrystalline nanostructures were produced from commercial SnO powders in a new system that combines a low-temperature plasma with heating. The method has the potential to improve the initial efficiency and the cycling performance of SnO2 anodes in Li-ion batteries. With this system, the temperature of the SnO to SnO2 conversion was lowered from 430 to 320 °C, up to 5 at% of doped nitrogen was detected and a nano-scale polycrystalline structure was observed in the product. Combining heat and low-pressure plasma is a promising approach for the production and treatment of enhanced energy storage materials.

Effect of sintering temperature on electrochemical performance of LiFe0·4Mn0·6PO4/C cathode materials

Carbon coated LiFe0·4Mn0·6PO4 (LiFe0·4Mn0·6PO4/C) was synthesised using high energy ball milling and annealing processes. The starting materials of Li2C2O4, FeC2O4.2H2O, MnC2O4.2H2O, NH4H2PO4 were firstly milled for 40 h, and followed by further milling for 5 h after adding glucose solution. The milled sample was heated at different temperatures (550, 600, 650 and 700°C) for 10 h to produce LiFe0·4Mn0·6PO4/C composites. The structure and morphology of the samples were investigated using X-ray diffraction, field emission scanning electron microscopy, and high resolution electron microscopy. The phase of samples annealed at 550 and 600°C mainly consists of olivine type LiFePO4, but a small amount of Fe2P impurity phase is formed in the samples annealed at 650 and 700°C. Electrochemical analysis results show that LiFe0·4Mn0·6PO4/C synthesised at 600°C exhibits the best performance with the initial discharge capacity of 128 mAh g-1 at 0·1 C, and 109 mAh g-1 at 1 C after 500 cycles. The LiFe0·4Mn0·6PO4/C exhibits excellent electrochemical properties for high energy density lithium ion batteries.

Ionic conductivity and molecular dynamic behavior in supramolecular ionic networks; the effect of lithium salt addition

Supramolecular ionic networks combine singular properties such as self-healing behaviour and ionic conductivity. In this work we present an insight into the ionic conductivity and molecular dynamic behaviour of an amorphous and semicrystalline supramolecular ionic networks (iNets) that were synthesised by self-assembly of difunctional imidazolium dicationic molecules coupled with (trifluoromethane-sulfonyl) imide dianionic molecules. Relatively low ionic conductivity values were obtained for the semicrystalline iNet below its melting point (Tm =101°C) in comparison with the amorphous iNet for which the conductivity significantly increased (~3 orders of magnitude) above 100°C. Upon LiTFSI doping, the semicrystalline iNet reached conductivity values ~ 10-3 Scm-1 due to enhanced mobility of the network which was supported by solid-state static NMR. Furthermore, the overlapping of 19F and 7Li resonance lines from both the semicrystalline network and the LiTFSI suggests fast molecular motions.

Electrochemical and physicochemical properties of small phosphonium cation ionic liquid electrolytes with high lithium salt content

Electrolytes of a room temperature ionic liquid (RTIL), trimethyl(isobutyl)phosphonium (P111i4) bis(fluorosulfonyl)imide (FSI) with a wide range of lithium bis(fluorosulfonyl)imide (LiFSI) salt concentrations (up to 3.8 mol kg−1 of salt in the RTIL) were characterised using a combination of techniques including viscosity, conductivity, differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), nuclear magnetic resonance (NMR) and cyclic voltammetry (CV). We show that the FSI-based electrolyte containing a high salt concentration (e.g. 1:1 salt to IL molar ratio, equivalent to 3.2 mol kg−1 of LiFSI) displays unusual transport behavior with respect to lithium ion mobility and promising electrochemical behavior, despite an increase in viscosity. These electrolytes could compete with the more traditionally studied nitrogen-based ionic liquids (ILs) in lithium battery applications.

Biocompatible ionic liquid-biopolymer electrolyte-enabled thin and compact magnesium-air batteries.

With the surge of interest in miniaturized implanted medical devices (IMDs), implantable power sources with small dimensions and biocompatibility are in high demand. Implanted battery/supercapacitor devices are commonly packaged within a case that occupies a large volume, making miniaturization difficult. In this study, we demonstrate a polymer electrolyte-enabled biocompatible magnesium-air battery device with a total thickness of approximately 300 μm. It consists of a biocompatible polypyrrole-para(toluene sulfonic acid) cathode and a bioresorbable magnesium alloy anode. The biocompatible electrolyte used is made of choline nitrate (ionic liquid) embedded in a biopolymer, chitosan. This polymer electrolyte is mechanically robust and offers a high ionic conductivity of 8.9 × 10(-3) S cm(-1). The assembled battery delivers a maximum volumetric power density of 3.9 W L(-1), which is sufficient to drive some types of IMDs, such as cardiac pacemakers or biomonitoring systems. This miniaturized, biocompatible magnesium-air battery may pave the way to a future generation of implantable power sources.