Synthesis of LiFePO4@carbon nanotube core-shell nanowires with a high-energy efficient method for superior lithium ion battery cathodes

A high-energy efficient method is developed for the synthesis of LiFePO4@CNT core-shell nanowire structures. The method consists of two steps: liquid deposition approach to prepare FePO4@CNT core-shell nanowires and solvothermal lithiation to obtain the LiFePO4@CNT core-shell nanowires at a low temperature. The solution phase method can be easily scaled up for commercial application. The performance of the materials produced by this method is evaluated in Li ion batteries. The one-dimensional LiFePO4@CNT nanowires offer a stable and efficient backbone for electron transport. The LiFePO4@CNT core-shell nanowires exhibit a high capacity of 132.8 mAh g^-1 at a rate of 0.2C, as well as high rate capability (64.4 mAh g^-1 at 20C) for Li ion storage.

Study on LiFe1 − xSm xPO4/C used as cathode materials for lithium-ion batteries with low Sm component

LiFe1 − xSmxPO4/C cathode materials were synthesized though a facile hydrothermal method. Compared with high-temperature solid-phase sintering, the method can allow for the fabrication of low Sm content (2 %), a scarce and expensive rare earth element, while the presence of an optimized carbon coating with large amount of sp²-type carbon sharply increases the material’s electrochemical performance. The high-rate dischargeability at 5 C, as well as the exchange current density, can be increased by 21 and 86 %, respectively, which were attributed to the fine size and the large cell parameter a/c as much. It should be pointed out that the a/c value will be increased for the LiFePO4 Sm-doped papered by both of the two methods, while the mechanism is different: The value c is increased for the front and the value a is decreased for the latter, respectively.

Characterisation of ion transport in sulfonate based ionomer systems containing lithium and quaternary ammonium cations

Two sulfonated ionomers based on poly(triethylmethyl ammonium 2-acrylamido-2-methyl-1-propane sulfonic acid) (PAMPS) and containing mixtures of Li⁺ and quaternary ammonium cations are characterised. The first system contains Li⁺ and the methyltriethyl ammonium cation (N1222) in a 1:9 molar ratio, and the ⁷Li NMR line widths showed that the Li⁺ ions are mobile in this system below the glass transition temperature (105°C) and are therefore decoupled from the polymer segmental motion. The conductivity in this system was measured as 10^-5 Scm^-1 at 130°C. A second PAMPS system containing Li⁺ and the dimethylbutylmethoxyethyl ammonium cation (N114(2O1)) in a 2:8 molar ratio showed much lower conductivities despite a significantly lower Tg (60°C), possibly due to associations between the Li⁺ and the ether group on the ammonium cation, or between the latter cations and the sulfonate groups.

Nanostructured composite anodes and cathodes for lithium-ion and sodium-ion batteries

The thesis was focused on developing alloy based anode materials for Li-ion and Na-ion batteries. It helps to reduce the size and increase the energy density of the batteries. Furthermore, a novel cathode material was developed for Na-ion batteries which showed good cycling performance over a period of 100 cycles.

Improvement of charge/discharge properties of oligoether electrolytes by zwitterions with an attached cyano group for use in lithium-ion secondary batteries

Zwitterions with a cyano group on the side chain (CZ) were synthesized. Although the addition of CZ caused a slightly negative effect on viscosity, ionic conductivity, limiting current density, and lithium transference number, the oxidation limit of PEGDME/lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) composites was improved to over 5 V. For charge/discharge testing using Li|electrolyte|LiCoO2 cells, the cycle stability of PEGDME/LiTFSA with CZ in the voltage range of 3.0-4.6 V was much higher than that of PEGDME/LiTFSA. Incorporating a small mole fraction of CZ into PEGDME-based electrolytes prevented an increase in the interface resistance between the electrolyte and cathode with increasing numbers of the cycle.

Understanding structure-function relationship in hybrid Co3O4-Fe2O3/C lithium-ion battery electrodes

A range of high-capacity Li-ion anode materials (conversion reactions with lithium) suffer from poor cycling stability and limited high-rate performance. These issues can be addressed through hybridization of multiple nanostructured components in an electrode. Using a Co3O4-Fe2O3/C system as an example, we demonstrate that the cycling stability and rate performance are improved in a hybrid electrode. The hybrid Co3O4-Fe2O3/C electrode exhibits long-term cycling stability (300 cycles) at a moderate current rate with a retained capacity of approximately 700 mAh g(-1). The reversible capacity of the Co3O4-Fe2O3/C electrode is still about 400 mAh g(-1) (above the theoretical capacity of graphite) at a high current rate of ca. 3 A g(-1), whereas Co3O4-Fe2O3, Fe2O3/C, and Co3O4/C electrodes (used as controls) are unable to operate as effectively under identical testing conditions. To understand the structure-function relationship in the hybrid electrode and the reasons for the enhanced cycling stability, we employed a combination of ex situ and in situ techniques. Our results indicate that the improvements in the hybrid electrode originate from the combination of sequential electrochemical activity of the transition metal oxides with an enhanced electronic conductivity provided by percolating carbon chains.

Olanzapine or chlorpromazine plus lithium in first episode psychotic mania: An 8-week randomised controlled trial

BACKGROUND: Treatment strategies for mental disorders may vary according to illness stage. However no data currently exist to guide treatment in first episode psychotic mania. The aim of this study was to compare the safety and efficacy profile of chlorpromazine and olanzapine, as add-on to lithium, in patients with a first episode of psychotic mania, expecting better safety profile and adherence to olanzapine but similar efficacy for both treatments. METHODS: Data from 83 patients were collected in an 8-week randomised controlled trial on clinical variables, side effects, vital signs, and weight. Analyses of treatment differences over time were based on intent-to-treat principles. Kaplan-Meier estimated survival curves were used to analyse time-to-event data and mixed effects models repeated measures analysis of variance were used to determine treatment group differences over time on safety and efficacy measures. RESULTS: Ethics committee approval to delay informed consent procedure until recovery from the acute episode allowed the inclusion of 83 patients highly representative of those treated in the public sector. Contrary to our hypotheses, safety profile of both medications was similar. A signal for higher rate (P=.032) and earlier occurrence (P=.043) of mania remission was observed in the olanzapine group which did not survive correction for multiple comparisons. CONCLUSIONS: Olanzapine and chlorpromazine have a similar safety profile in a uniquely representative cohort of patients with first episode psychotic mania. The possibility for a greater impact of olanzapine on manic symptoms leading to earlier remission of the episode needs exploration in a large sample.

A single-blind, randomised controlled trial on the effects of lithium and quetiapine monotherapy on the trajectory of cognitive functioning in first episode mania: A 12-month follow-up study

BACKGROUND: Cognitive deficits have been reported during the early stages of bipolar disorder; however, the role of medication on such deficits remains unclear. The aim of this study was to compare the effects of lithium and quetiapine monotherapy on cognitive performance in people following first episode mania. METHODS: The design was a single-blind, randomised controlled trial on a cohort of 61 participants following first episode mania. Participants received either lithium or quetiapine monotherapy as maintenance treatment over a 12-month follow-up period. The groups were compared on performance outcomes using an extensive cognitive assessment battery conducted at baseline, month 3 and month 12 follow-up time-points. RESULTS: There was a significant interaction between group and time in phonemic fluency at the 3-month and 12-month endpoints, reflecting greater improvements in performance in lithium-treated participants relative to quetiapine-treated participants. After controlling for multiple comparisons, there were no other significant interactions between group and time for other measures of cognition. CONCLUSION: Although the effects of lithium and quetiapine treatment were similar for most cognitive domains, the findings imply that early initiation of lithium treatment may benefit the trajectory of cognition, specifically verbal fluency in young people with bipolar disorder. Given that cognition is a major symptomatic domain of bipolar disorder and has substantive effects on general functioning, the ability to influence the trajectory of cognitive change is of considerable clinical importance.

Self-assembled V2O5 interconnected microspheres produced in a fish-water electrolyte medium as a high-performance lithium-ion-battery cathode

Interconnected microspheres of V2O5 composed of ultra-long nanobelts are synthesized in an environmental friendly way by adopting a conventional anodization process combined with annealing. The synthesis process is simple and low-cost because it does not require any additional chemicals or reagents. Commercial fish-water is used as an electrolyte medium to anodize vanadium foil for the first time. Electron microscopy investigation reveals that each belt consists of numerous nanofibers with free space between them. Therefore, this novel nanostructure demonstrates many outstanding features during electrochemical operation. This structure prevents self-aggregation of active materials and fully utilizes the advantage of active materials by maintaining a large effective contact area between active materials, conductive additives, and electrolyte, which is a key challenge for most nanomaterials. The electrodes exhibit promising electrochemical performance with a stable discharge capacity of 227 mAh·g–1 at 1C after 200 cycles. The rate capability of the electrode is outstanding, and the obtained capacity is as high as 278 at 0.5C, 259 at 1C, 240 at 2C, 206 at 5C, and 166 mAh·g–1 at 10C. Overall, this novel structure could be one of the most favorable nanostructures of vanadium oxide-based cathodes for Li-ion batteries. [Figure not available: see fulltext.]

Synthesis of an indium oxide nanoparticle embedded graphene three-dimensional architecture for enhanced lithium-ion storage

Indium oxide nanoparticles were synthesised by using a facile and scalable strategy. The as-prepared nanoparticles (20-40 nm) were in situ and homogeneously distributed in a three-dimensional (3D) graphene architecture subsequently during the fabrication process. The obtained nanocomposite acts as a high capacity anode material for lithium-ion batteries and demonstrates good cycle stability. A drastically enhanced capacity of 750 mA h g^-1 in comparison with that of bare In2O3 nanoparticles can be maintained after 100 cycles, along with an improved high rate performance (210 mA h g^-1 at 1 A g^-1 and 120 mA h g^-1 at 2 A g^-1). The excellent performance is linked with the indium oxide nanoparticles and the unique 3D interconnected porous graphene structure. The highly conductive and porous 3D graphene structure greatly enhances the performance of lithium-ion batteries by protecting the nanoparticles from the electrolyte, stabilizing the nanoparticles during cycles and buffering the volume expansion upon lithium insertion.

Advanced N-doped mesoporous molybdenum disulfide nanosheets and the enhanced lithium-ion storage performance

With the increasing interest in two-dimensional van der Waals materials, molybdenum disulfide (MoS2) has emerged as a promising material for electronic and energy storage devices. It suffers from poor cycling stability and low rate capability when used as an anode in lithium ion batteries. Here, N-doped MoS2 nanosheets with 2-8 atomic layers, increased interlayer distance, mesoporous structure and high surface area synthesised by a simple sol-gel method show an enhanced lithium storage performance, delivering a high reversible capacity (998.0 mA h g-1, 50 mA g-1), high rate performance (610 mA h g-1, 2 A g-1), and excellent cycling stability. The excellent lithium storage performance of the MoS2 nanosheets might be due to the better electrical and ionic conductivity and improved lithium ion diffusion which are related to their structural characteristics and high concentration N doping. The possible mechanism of the improved performance is proposed and discussed.

N7-(carboxymethyl)guanine-lithium crystalline complex: a bioinspired solid electrolyte

Electrochemical device with components having direct significance to biological life processes is a potent futuristic strategy for the realization of all-round green and sustainable development. We present here synthesis design, structural analysis and ion transport of a novel solid organic electrolyte (G7Li), a compound reminiscent of ion channels, derived from regioisomeric N7-guanine-carboxylate conjugate and Li-ions. G7Li, with it's in-built supply of Li(+)-ions, exhibited remarkably high lithium-ion transference number (= 0.75) and tunable room temperature ionic conductivity spanning three decades (≈10(-7) to 10(-3) Ω(-1) cm(-1)) as a function of moisture content. The ionic conductivity show a distinct reversible transition around 80-100 °C, from a dual Li(+) and H(+) (<100 °C) to a pure Li(+) conductor (>100 °C). Systematic studies reveal a transition from water-assisted Li-ion transport to Li hopping-like mechanism involving guanine-Li coordination. While as-synthesized G7Li has potential in humidity sensors, the anhydrous G7Li is attractive for rechargeable batteries.

Lithium-ion capacitors with 2D Nb2CTx (MXene) - carbon nanotube electrodes

There is a growing interest to hybrid energy storage devices, such as lithium-ion capacitors, in which battery-type electrodes are combined with capacitor-type ones. It is anticipated that the energy density (either gravimetric or volumetric) of lithium-ion capacitors is improved if pseudocapacitive or fast insertion materials are used instead of conventional activated carbon (AC) in the capacitor-type electrode. MXenes, a new family of two-dimensional transition metal carbides, demonstrate metallic conductivity and fast charge-discharge behavior that make them suitable for this application. In this study, we move beyond single electrodes, half-cell studies and demonstrate three types of hybrid cells using Nb2CTx-carbon nanotube (CNT) films. It is shown that lithiated graphite/Nb2CTx-CNT, Nb2CTx-CNT/LiFePO4 and lithiated Nb2CTx-CNT/Nb2CTx-CNT cells are all able to operate within 3 V voltage windows and deliver capacities of 43, 24 and 36 mAh/g (per total weight of two electrodes), respectively. Moreover, the polarity of the electrodes can be reversed in the symmetric Nb2CTx-CNT cells from providing a positive potential between 0 and 3 V to a negative one from -3 to 0 V. It is shown that the volumetric energy density (50-70 Wh/L) of our first-generation devices with MXene electrodes exceeds that of a lithium titanate/AC capacitor.

Synthesis of a porous sheet-like V₂O₅-CNT nanocomposite using an ice-templating 'bricks-and-mortar' assembly approach as a high-capacity, long cyclelife cathode material for lithium-ion batteries

Tailoring the nanostructures of electrode materials is an effective way to enhance their electrochemical performance for energy storage. Herein, an ice-templating "bricks-and-mortar" assembly approach is reported to make ribbon-like V2O5 nanoparticles and CNTs integrated into a two-dimensional (2D) porous sheet-like V2O5-CNT nanocomposite. The obtained sheet-like V2O5-CNT nanocomposite possesses unique structural characteristics, including a hierarchical porous structure, 2D morphology, large specific surface area and internal conducting networks, which lead to superior electrochemical performances in terms of long-term cyclability and significantly enhanced rate capability when used as a cathode material for LIBs. The sheet-like V2O5-CNT nanocomposite can charge/discharge at high rates of 5C, 10C and 20C, with discharge capacities of approximately 240 mA h g-1, 180 mA h g-1, and 160 mA h g-1, respectively. It also retains 71% of the initial discharge capacity after 300 cycles at a high rate of 5C, with only 0.097% capacity loss per cycle. The rate capability and cycling performance of the sheet-like V2O5-CNT nanocomposite are significantly better than those of commercial V2O5 and most of the reported V2O5 nanocomposite.

In situ prepared V2O5/graphene hybrid as a superior cathode material for lithium-ion batteries

Developing synthetic methods for graphene based cathode materials, with low cost and in an environmentally friendly way, is necessary for industrial production. Although the precursor of graphene is abundant on the earth, the most common precursor of graphene is graphene oxide (GO), and it needs many steps and reagents for transformation to graphite. The traditional approach for the synthesis of GO needs many chemicals, thus leading to a high cost for production and potentially great amounts of damage to the environment. In this study, we develop a simple wet ball-milling method to construct a V2O5/graphene hybrid structure in which nanometre-sized V2O5 particles/aggregates are well embedded and uniformly dispersed into the crumpled and flexible graphene sheets generated by in situ conversion of bulk graphite. The combination of V2O5 nanoparticles/aggregates and in situ graphene leads the hybrid to exhibit a markedly enhanced discharge capacity, excellent rate capability, and good cycling stability. This study suggests that nanostructured metal oxide electrodes integrated with graphene can address the poor cycling issues of electrode materials that suffer from low electronic and ionic conductivities. This simple wet ball-milling method can potentially be used to prepare various graphene based hybrid electrodes for large scale energy storage applications.