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.

The study of metal nitride layer formation by solid-state reactions

A new solid-state reaction to form metal nitrides has been investigated. It was confirmed that single phase chromium nitride is formed by a solid-state diffusion reaction between iron nitride and chromium chloride powders at temperatures between 570-700°C. The discovered reaction can be applied to form chromium nitride coatings on tool steels for metal forming applications.

Phosphorus-carbon nanocomposite anodes for lithium-ion and sodium-ion batteries

With the expected theoretical capacity of 2596 mA h g-1, phosphorus is considered to be the highest capacity anode material for sodium-ion batteries and one of the most attractive anode materials for lithium-ion systems. This work presents a comprehensive study of phosphorus-carbon nanocomposite anodes for both lithium-ion and sodium-ion batteries. The composite electrodes are able to display high initial capacities of approximately 1700 and 1300 mA h g-1 in lithium and sodium half-cells, respectively, when the cells are tested within a larger potential windows of 2.0-0.01 V vs. Li/Li+ and Na/Na+. The level of demonstrated capacity is underpinned by the storage mechanism, based on the transformation of phosphorus to Li3P phase for lithium cells and an incomplete transformation to Na3P phase for sodium cells. The capacity deteriorates upon cycling, which is shown to originate from disintegration of electrodes and their delamination from current collectors by post-cycling ex situ electron microscopy. Stable cyclic performance at the level of ∼700 and ∼350-400 mA h g-1 can be achieved if the potential windows are restricted to 2.0-0.67 V vs. Li/Li+ for lithium and 2-0.33 vs. Na/Na+ for sodium half-cells. The results are critically discussed in light of existing literature reports

Ex situ electrochemical sodiation/desodiation observation of Co₃O₄ anchored carbon nanotubes: a high performance sodium-ion battery anode produced by pulsed plasma in a liquid

Liquid plasma, produced by nanosecond pulses, provides an efficient and simple way to fabricate a nanocomposite architecture of Co3O4/CNTs from carbon nanotubes (CNTs) and clusters of Co3O4 nanoparticles in deionized water. The crucial feature of the composite's structure is that Co3O4 nanoparticle clusters are uniformly dispersed and anchored to CNT networks in which Co3O4 guarantees high electrochemical reactivity towards sodium, and CNTs provide conductivity and stabilize the anode structure. We demonstrated that the Co3O4/CNT nanocomposite is capable of delivering a stable and high capacity of 403 mA h g(-1) at 50 mA g(-1) after 100 cycles where the sodium uptake/extract is confirmed in the way of reversible conversion reaction by adopting ex situ techniques. The rate capability of the composite is significantly improved and its reversible capacity is measured to be 212 mA h g(-1) at 1.6 A g(-1) and 190 mA h g(-1) at 3.2 A g(-1), respectively. Due to the simple synthesis technique with high electrochemical performance, Co3O4/CNT nanocomposites have great potential as anode materials for sodium-ion batteries.

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.

Solid-state NMR as a probe of anion binding: molecular dynamics and associations in a [5]polynorbornane bisurea host complexed with terephthalate

A range of solid-state NMR techniques is used to characterise a molecular host:guest complex consisting of a [5]polynorbornane bisurea host binding a terephthalate dianion guest. Detailed information is obtained on the molecular dynamics and associations from the point of view of both the host and guest molecules. The formation of the complex in the solid state is confirmed using (1)H 2D exchange NMR, and the 180° flipping of the (2)H-labelled terephthalate guest and its eventual expulsion from the complex at elevated temperatures are quantified using variable-temperature (2)H spin-echo experiments. Two-dimensional (1)H-(13)C HETCOR spectra obtained under fast magic angle spinning conditions (60 kHz) show a high resolution despite the poor crystallinity of the solid complex, and clearly reveal changes in the rigidity of the host molecule when complexed. Short-range intra- and intermolecular (1)H-(1)H proximities are also detected using 2D SQ-DQ correlation methods, providing insight into the molecular packing in the solid phase.

High-performance flexible all-solid-state supercapacitor from large free-standing graphene-PEDOT/PSS films

Although great attention has been paid to wearable electronic devices in recent years, flexible lightweight batteries or supercapacitors with high performance are still not readily available due to the limitations of the flexible electrode inventory. In this work, highly flexible, bendable and conductive rGO-PEDOT/PSS films were prepared using a simple bar-coating method. The assembled device using rGO-PEDOT/PSS electrode could be bent and rolled up without any decrease in electrochemical performance. A relatively high areal capacitance of 448 mF cm(-2) was achieved at a scan rate of 10 mV s(-1) using the composite electrode with a high mass loading (8.49 mg cm(-2)), indicating the potential to be used in practical applications. To demonstrate this applicability, a roll-up supercapacitor device was constructed, which illustrated the operation of a green LED light for 20 seconds when fully charged.

Ultra-wideline 14N solid-state NMR as a method for differentiating polymorphs: glycine as a case study

Nitrogen-14 solid-state NMR (SSNMR) is utilized to differentiate three polymorphic forms and a hydrochloride (HCl) salt of the amino acid glycine. Frequency-swept Wideband, Uniform Rate, Smooth Truncated (WURST) pulses were used in conjunction with Carr-Purcell Meiboom-Gill refocusing, in the form of the WURST-CPMG pulse sequence, for all spectral acquisitions. The ¹⁴N quadrupolar interaction is shown to be very sensitive to variations in the local electric field gradients (EFGs) about the ¹⁴N nucleus; hence, differentiation of the samples is accomplished through determination of the quadrupolar parameters CQ and ηQ, which are obtained from analytical simulations of the ¹⁴N SSNMR powder patterns of stationary samples (i.e., static NMR spectra). Additionally, differentiation of the polymorphs is also possible via the measurement of ¹⁴N effective transverse relaxation time constants, T^eff2(¹⁴N). Plane-wave density functional theory (DFT) calculations, which exploit the periodicity of crystal lattices, are utilized to confirm the experimentally determined quadrupolar parameters as well as to determine the orientation of the ¹⁴N EFG tensors in the molecular frames. Several signal-enhancement techniques are also discussed to help improve the sensitivity of the ¹⁴N SSNMR acquisition method, including the use of selective deuteration, the application of the BRoadband Adiabatic INversion Cross-Polarization (BRAIN-CP) technique, and the use of variable-temperature (VT) experiments. Finally, we examine several cases where ¹⁴N VT experiments employing Carr-Purcell-Meiboom-Gill (CPMG) refocusing are used to approximate the rotational energy barriers for RNH3⁺ groups.

Polymer architecture effect on sodium ion transport in PSTFSI-based ionomers: a molecular dynamics study

In this study, we investigated the effect of polymer architecture on the ion dynamics and local structure to understand the factors that might lead to the design of highly conductive and mechanically robust polyelectrolytes. Molecular dynamic simulations were undertaken on the sodium poly[(4-styrenesulfonyl) (trifluoromethanesulfonyl) imide] P(STFSINa) homopolymer and its copolymers with either ether or styrene spacer groups to investigate the spacer length and polarity dependence of Na-ion transport. Using a scaled charge model, we observed a continuous ion aggregate network in the homopolymer, which facilitates the fast ion dynamics despite the rigid polymer matrix. The longest spacer groups disrupt this percolating ionic network differently, with the ether group being more disruptive than the styrene group, and leading to more discrete ionic aggregates. The copolymer with the ether spacer was also found to result in an alternative Na-ion diffusion mechanism.

Investigating non-fluorinated anions for sodium battery electrolytes based on ionic liquids

In order for sodium batteries to become a safe, lower cost option for large scale energy storage, minimising the price of all components is important. We report here on the application of a pyrrolidinium room temperature ionic liquid comprising the dicyanamide anion as a successful electrolyte system for sodium metal batteries that does not contain expensive fluorinated species. The effects of plating/stripping of sodium from Na metal electrodes has been investigated in a symmetrical Na | electrolyte | Na configuration at a current density of 10 μA cm− 2. Comparisons are drawn to reference organic electrolytes comprising propylene carbonate-fluoroethylene carbonate. Residual water molecules in the ionic liquid electrolyte are observed to have a significant effect upon the surface film and subsequent favourable plating/stripping behaviour of symmetrical cells and this is explored in detail. An increase of the moisture content from 90 ppm to 400 ppm impedes both electrodeposition and electrodissolution of the Na+/Na. This is investigated at Ni electrodes using cyclic voltammetry at different Na+-salt concentrations to further understand the mechanism.

Increased ion conduction in dual cation [sodium][tetraalkylammonium] poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide-co-ethylacrylate] ionomers

© The Royal Society of Chemistry. Solid-state polymer electrolytes, as an alternative to traditional liquid electrolytes, have been intensively investigated for energy conversion and storage devices. The transport rate of single ions is the key to their high performance. For application in emerging sodium batteries, we have developed three dual-cation polymeric ionomers, which contain bulky tetraalkylammonium ions in addition to the sodium ion. The sizes and relative contents of the ammonium ions vary relative to the sodium ion contents. Comparative studies of ion dynamics, thermal properties, phase behaviours and ionic conductivities were carried out, taking advantage of various spectroscopic and thermal chemistry methods. The ion conductivities of the ionomers are greatly enhanced by the introduction of bulky counterions, as a result of the additional free volume and decreased sodium ion association. Raman spectroscopy and thermal analysis as well as the solid-state nuclear magnetic resonance studies are used to probe the conductivity behaviour.