Electrochemical investigation of sodium reactivity with nanostructured Co3O4 for sodium-ion batteries

The electrochemical behaviour of Co3O4 with sodium is reported here. Upon cycling in the voltage window of 0.01–3.0 V, Co3O4 undergoes a conversion reaction and exhibits a reversible capacity of 447 mA h g−1 after 50 cycles. Therefore, nanostructured Co3O4 presents feasible electrochemical sodium storage, offering possibilities to develop new anode materials for sodium-ion batteries.

Biotemplated fabrication of a novel hierarchical porous C/LiFePO4/C composite for Li-ion batteries

Hierarchical porous composites are a potentially attractive material for high-rate cathode. This work presents a facile sol-gel process for the fabrication of a hierarchical porous C/LiFePO4/bio-C composite by using artemia cyst shells as natural biological carbon templates. The C/LiFePO4/bio-C composite exhibits a superior electrochemical performance with discharge capacities of 105 mA h g-1, 93 mA h g-1 and 80 mA h g-1 at 5 C, 10 C and 20 C, respectively. Remarkably, it produces a high discharge capacity of 69.1 mA h g-1 and no fading after 50 cycles even at a high current density of 6800 mA g-1. This journal is

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.

Sulfur-impregnated, sandwich-type, hybrid carbon nanosheets with hierarchical porous structure for high-performance lithium-sulfur batteries

Sandwich-type hybrid carbon nanosheets (SCNMM) consisting of graphene and micro/mesoporous carbon layer are fabricated via a double template method using graphene oxide as the shape-directing agent and SiO2 nanoparticles as the mesoporous guide. The polypyrrole synthesized in situ on the graphene oxide sheets is used as a carbon precursor. The micro/mesoporous strcutures of the SCNMM are created by a carbonization process followed by HF solution etching and KOH treatment. Sulfur is impregnated into the hybrid carbon nanosheets to generate S@SCNMM composites for the cathode materials in Li-S secondary batteries. The microstructures and electrochemical performance of the as-prepared samples are investigated in detail. The hybrid carbon nanosheets, which have a thickness of about 10-25 nm, high surface area of 1588 m2 g-1, and broad pore size distribution of 0.8-6.0 nm, are highly interconnected to form a 3D hierarchical structure. The S@SCNMM sample with the sulfur content of 74 wt% exhibits excellent electrochemical performance, including large reversible capacity, good cycling stability and coulombic efficiency, and good rate capability, which is believed to be due to the structure of hybrid carbon materials with hierarchical porous structure, which have large specific surface area and pore volume.

Large-scale production of h-In2O3/carbon nanocomposites with enhanced lithium storage properties

h-In2O3/carbon nanocomposites were obtained via a facile ball milling process from a mixture of h-In2O3 nanoparticles and Super P carbon. Compared to pure h-In2O3 nanoparticles, the nanocomposites exhibited an initial discharge capacity of 1360 mAh g-1, a stable reversible capacity of 867 mAh g-1 after 100 cycles as well as a high coulombic efficiency of 99%. The superior lithium-ion battery performance can be attributed to the specific structure of h-In2O3 and the uniform and continuous nano-carbon coating layers. The nano-carbon coating could protect the inner active materials from fragmentation and increase the electronic conductivity. This study not only provides a promising electrode material for high-performance lithium-ion batteries, but also further demonstrates a straightforward, effective and environmental friendly process for synthesizing nanocomposites. © 2014 Elsevier Ltd.

Enhanced lithium storage in ZnFe2O4-C nanocomposite produced by a low-energy ball milling

Preparation of novel nanocomposite structure of ZnFe2O4-C is achieved by combining a sol-gel and a low energy ball milling method. The crucial feature of the composite's structure is that sol-gel synthesised ZnFe2O4 nanoparticles are dispersed and attached uniformly along the chains of Super P Li™ carbon black matrix by adopting a low energy ball milling. The composite ZnFe2O4-C electrodes are capable of delivering a very stable reversible capacity of 681 mAh g-1 (96% retention of the calculated theoretical capacity of ∼710 mAh g-1) at 0.1 C after 100 cycles with a remarkable Coulombic efficiency (82%) improvement in the first cycle. The rate capability of the composite is significantly improved and obtained capacity was as high as 702 at 0.1, 648 at 0.5, 582 at 1, 547 at 2 and 469 mAh g-1 at 4 C (2.85 A g-1), respectively. When cell is returned to 0.1 C, the capacity recovery was still ∼98%. Overall, the electrochemical performance (in terms of cycling stability, high rate capability, and capacity retention) is outstanding and much better than those of the related reported works. Therefore, our smart electrode design enables ZnFe2O4-C sample to be a high quality anode material for lithium-ion 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.

Unexpected effect of tetraglyme plasticizer on lithium ion dynamics in PAMPS based ionomers

Li(+) cation conducting ionomers based on poly(2-acrylamido-2-methyl-1-propane sulphonic acid) (PAMPS) incorporating a low molecular weight plasticizer have been characterized. Previously we have observed an apparent decoupling of ionic conductivity and lithium ion dynamics from the Tg of this ionomer along with an increase in ionic conductivity obtained by incorporating a quaternary ammonium co-cation. The incorporation of tetraglyme as a coordinating plasticizer was investigated in order to further improve the ion dissociation and dynamics. Solid-state NMR, thermal analysis, impedance spectroscopy and infrared spectroscopy were used to characterize these systems. As expected, the glass transition temperature Tg decreased upon the addition of the plasticizer. However, in contrast to the previously reported Na-conducting systems, the ionic conductivity was also decreased by several orders of magnitude, indicating that the tetraglyme recouples the conductivity back to the polymer dynamics. Temperature dependent (7)Li NMR line width and T1 measurements were used to probe the Li(+) dynamics, which were found to be dependent on the Li(+) concentration, the nature of the co-cation and the presence or absence of tetraglyme.

Tin-based composite anodes for potassium-ion batteries

The electrochemical behaviour of a Sn-based anode in a potassium cell is reported for the first time. The material is active at low potentials vs. K/K(+), and encouraging capacities of around 150 mA h g(-1) are recorded. Experimental evidence shows that Sn is capable of alloying/de-alloying with potassium in a reversible manner.

Organic ionic plastic crystals : recent advances

Investigations into the synthesis and utilisation of organic ionic plastic crystals have made significant progress in recent years, driven by a continued need for high conductivity solid state electrolytes for a range of electrochemical devices. There are a number of different aspects to research in this area; fundamental studies, utilising a wide range of analytical techniques, of both pure and doped plastic crystals, and the development of plastic crystal-based materials as electrolytes in, for example, lithium ion batteries. Progress in these areas is highlighted and the development of new organic ionic plastic crystals, including a new class of proton conductors, is discussed.

Nanorods of vanadium compounds: synthesis, characterisation, and application in electrochemical energy storage

The synthesis and characterisation of nanorods of vanadium pentoxide, V(2)O(5), vanadium trioxide, V(2)O(3), vanadium dioxide, VO(2)(B), and vanadium nitride, VN, are presented, and their application in electrochemical supercapacitors and lithium-ion batteries is outlined. Specifically, a novel method for the preparation of V(2)O(5) nanorods is discussed. It involves ball milling as a first step and controlled annealing as a second step. Nanorods of V(2)O(5) can be converted into those of other vanadium-related phases by simple chemical reduction treatments. Such chemical transformations are pseudomorphic and often topotactic, that is, the resulting nanorods belong to a different chemical phase but tend to retain the original morphology and preferential crystal orientation dictated by parent V(2)O(5) crystals.

The corresponding properties of nanorods for their prospective application in electrochemical energy storage (lithium-ion batteries and electrochemical supercapacitors) are discussed. The synthesised V(2)O(5) nanorods possess a stable cyclic behaviour when they are used in a cathode of a lithium-ion battery and are suitable for use in an anode. VN nanorods synthesised by NH(3) reduction of V(2)O(5) were found to possess pseudocapacitive properties in aqueous electrolytes.

Anisotropic MRI contrast reveals enhanced ionic transport in plastic crystals

Organic ionic plastic crystals (OIPCs) are attractive as solid-state electrolytes for electrochemical devices such as lithium-ion batteries and solar and fuel cells. OIPCs offer high ionic conductivity, nonflammability, and versatility of molecular design. Nevertheless, intrinsic ion transport behavior of OIPCs is not fully understood, and their measured properties depend heavily on thermal history. Solid-state magnetic resonance imaging experiments reveal a striking image contrast anisotropy sensitive to the orientation of grain boundaries in polycrystalline OIPCs. Probing triethyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1222FSI) samples with different thermal history demonstrates vast variations in microcrystallite alignment. Upon slow cooling from the melt, microcrystallites exhibit a preferred orientation throughout the entire sample, leading to an order of magnitude increase in conductivity as probed using impedance spectroscopy. This investigation describes both a new conceptual window and a new characterization method for understanding polycrystalline domain structure and transport in plastic crystals and other solid-state conductors.

Excellent electrochemical performance of LiFe0.4Mn0.6PO4 microspheres produced using a double carbon coating process

Composite LiFe0.4Mn0.6PO4/C microspheres are considered advanced cathode materials for electric vehicles and other high-energy density applications due to their advantages of high energy density and excellent cycling stability. LiFe0.4Mn0.6PO4/C microspheres have been produced using a double carbon coating process employing traditional industrial techniques (ball milling, spray-drying and annealing). The obtained LiFe0.4Mn0.6PO4 microspheres exhibit a high discharge capacity of around 166 mA h g-1 at 0.1 C and excellent rate capabilities of 132, 103, and 72 mA h g-1 at 5, 10, and 20 C, respectively. A reversible capacity of about 152 mA h g-1 after 500 cycles at a current density of 1 C indicates an outstanding cycling stability. The excellent electrochemical performance is attributed to the micrometer-sized spheres of double carbon-coated LiFe0.4Mn0.6PO4 nanoparticles with improved electric conductivity and higher Li ion diffusion coefficients, ensuring full redox reactions of all nanoparticles. The results show that the advanced high-energy density cathode materials can be produced using existing industry techniques.