Dendritic growth during charging period is one of the main barriers for the rechargeablity of conventional batteries. Additionally this phenomenon hinders the utilization of high energy density metal candidates by limiting the safety and allowable operating condition for these devices. We address the role of square wave pulse on the growth dynamics of dendrites in the continuum scale and large time periods by formulating an analytical criterion. Our dimension-free analysis permits the application our results to a variety of electrochemical systems in diverse scales.

Electrochemical energy storage has recently seen an exponential demand in the large-scale (power) grid storage sector. Earth abundant sodium-ion batteries are competent to enable this goal with economic viability. In a recent report in sodium-ion battery research, alluaudite framework Na2Fe2(SO4)3 has been reported with the highest Fe3+/Fe2+ redox potential (ca. 3.8 V, P. Barpanda, G. Oyama, S. Nishimura, S. C. Chung, and A. Yamada., Nature Commun. 5: 4358, 2014) with energy density comparable to the state-of-the-art Li-ion batteries. Material discovery is as essential as optimization of the existing materials to yield better performance for efficient energy storage. In a goal to optimize the synthesis of the reported alluaudite, this work first time reports the aqueous based Pechini synthesis for sodium metal sulphate alluaudite. It is a two-step method, where complexing agent plays a crucial role in holding the metal ions reserving their oxidation states. In the 2nd step, this complexing agent leaves the product with porous morphology. Taking advantage of its porous as well as 3D conductive framework, the complex attains fast electron/ion transport and sodium intercalation. Moreover, the single-phase reaction mechanism during sodium intercalation is reflected in its cycling property. It performs as a desirable cathode with operating potential as high as 3.7 V. While pursuing the synthesis, we observed an excess amount of sodium sulphate in the precursor mixture is needed to reduce the amount of impurities. To optimize the composition of the alluaudite phase and to explore novel compounds, we have carefully surveyed the Na2SO4-FeSO4 binary system. This work explores the possible compositional and structural flexibility in the Pechini synthesized alluaudites. A comparative study between compositional and redox activity in these samples will further inspire improvement of the alluaudite-type sodium metal sulphates for advanced sodium-ion batteries.

The development of efficient water oxidation catalyst is a major path to realize water splitting systems, which could benefit high performance and cost-effective metal-air batteries, fuel cells and solar energy conversion. To date, the rare crustal abundant platinum group metals rule this sector with Pt-alloys being the best for oxygen reduction reaction (ORR) and ruthenium oxides for oxygen evolution reaction (OER) in acidic solution. However, they show poor stability and are too expensive for large scale applications. Moreover, oxygen reduction in basic solutions can otherwise be catalysed by metal oxide with non-precious earth abundant transition metals (e.g. Fe, Co, Ni). Hence, there is a massive demand to explore noble metal free bifunctional electrocatalysts. In this work, we present the electrocatalytic activity of three cobalt based sodium phosphates namely NaCoPO4 (with one phosphate), Na2CoP2O7 (with two phosphate) NaFe2Co(PO4)3 (with three phosphate). Synthesized by solution combustion route, all these phosphates confirmed phase purity. NaCoPO4 and Na2CoP2O7 adopted orthorhombic structure with Pnma and Pna21 space group respectively; whereas NaFe2Co(PO4)3 crystallized in monoclinic (C2/c) framework. Electrocatalytic activity of these cobalt phosphates were inspected by linear sweep voltammetry with rotating disk electrode (RDE). All three showed promising bifunctional activity. In fact, the ORR activities of both orthorhombic cobalt phosphates are comparable to Vulcan carbon and Pt/C. OER activity of Na2CoP2O7 overrode other phosphates. The bifunctional activity and good stability of these sodium cobalt phosphates stem from cobalt ions and stabilization of the catalytic centres by the phosphate frameworks. The present work builds a detail structure-property correlation in these phosphate systems and also demonstrates the possibility of utilizing these sodium cobalt phosphates as alternate cost-effective, novel electrocatalysts for efficient OER/ORR activity in alkaline solution.

Among energy storage devices, the redox flow batteries are important for variety of applications such as for grid storage. In this class of batteries a large number of redox couples have been examined in the past. The vanadium redox couple, although is attractive for this application, suffers from a) poor charge transfer characteristics b) electrode degradation and c) deteriorating performance. We wish to report here that all these deficiencies have been overcome by using a graphene quantum dot electrodes. This electrode has the advantage of large surface area, high electrical and thermal conductivity. The cell voltage of 1.5 V and power density of about 120 mW/cm2 and coulombic efficiency of 90% can be achieved as the redox couples, V(IV)/V(V) and V(III)/V(II) undergo fast electron transfer at the interface of the quantum dots and solution resulting in higher reversibility. The cyclic voltammetric experiments carried out with quantum dots in the solutions during the oxidation of V(IV) show enhanced currents, due to the movements of the dots which is conducive for power gain in the battery operation. The electrochemical degradation is absent with the quantum dot electrode. The charge/discharge cycles have been reproducible.

The system of quinone molecules encapsulated in the single-wall carbon nanotube (SWCNT) has been proposed as a next-generation cathode electrode material for rechargeable battery. We investigate the complex interaction among the SWCNT, phenanthrene-quinone (PhQ), and Li atoms in the encapsulated system by using our original DFT code. We thereby find that the shape of the SWCNT changes significantly in the relaxed state depending on the extent of Li atoms inserted. The SWCNT shows a circular cylinder shape when no Li exists. With sufficient Li atoms inserted, the SWCNT is flattened. Substantial electron transfer from the PhQs to SWCNT is found. As for the dynamics of Li atoms in insertion or extraction process, we find that the Li atoms can take either of the two paths: one is along the inner wall of the SWCNT and the other is hopping on the PhQs.

Catalytic activity of conducting polymers in biofuel cells has been studied in comparison with the performance of Pt-black (Pt-B). The cells were direct and passive type with structure of biofuel/anode catalyst/Nafion®/cathode catalyst/air. Conducting polymers of polyaniline, polypyrrole and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT*PSS) were examined for the anode and cathode catalysts. L-ascorbic acid was used as the biofuel, and the Nafion® was served as a proton transfer membrane. In the standard Pt-B anode/Pt-B cathode cell, the typical Voc (open circuit voltage) = 0.52 V, ISC (short circuit current) = 8 mA/cm2 and the Pmax (maximum power density) of approximately 0.8 mW/cm2 were obtained. In a cell with catalysts of PEDOT*PSS anode/Pt-B cathode, Voc = 0.55 V and the maximum power density of 1.2 mW/cm2 were obtained, which were larger than that of the standard Pt-B/Pt-B cell. Polyaniline and Polypyrrole were also found to be a potential candidate for catalysts in biofuel cells.

Lithium ion batteries with high-rate performance have been demanded since electric and hybrid vehicles are released. It is known that high interfacial resistance between electrode and electrolyte prevents intercalation of lithium ions. We investigated high-rate capability of typical LiCoO2 cathode with various surface morphologies using epitaxial thin films prepared by pulsed laser deposition. As a result, high-rate performance in (104)LiCoO2 thin films was enhanced by an increase of (110)LiCoO2 facet density because diffusion coefficient of (110)LiCoO2 was larger than that of (104)LiCoO2. Therefore, a control of crystal plane at the surface is a key point for high-rate performance.

Due to extremely high conductivity of copper (Cu), copper–based nanocomposites offer remarkable opportunities for use in energy conversion and storage. Their applications demand low-cost syntheses routes relying on using inexpensive equipment with no formation of hazardous wastes. In this work, we report on a novel, cheap and environmentally friendly synthesis and application of nano-porous Cu as a support for lithium titanate. The infiltration of lithium titanate onto the inner surface of NPCu produced high-rate anodes for Li-ion batteries capable of providing nearly 50mAh/g during about 20s charging while retaining about 70% of the initial capacity after 1000 charge-discharge cycles. The demonstrated versatility and simplicity of this fascinating approach show great promises for scalable production and the use of NPCu in various cost-sensitive applications.

Understanding the structural evolution of electrode material during electrochemical activity is important to elucidate the mechanism of (de)lithiation, and improve the electrochemical function based on the material properties. In this study, lithium vanadium oxide (LVO, LiV3O8) was investigated using ex-situ, in-situ, and operando experiments. Via a combination of in-situ X-ray diffraction (XRD) and density functional theory results, a reversible structural evolution during lithiation was revealed: from Li poor α phase (LiV3O8) to Li rich α phase (Li2.5V3O8) and finally β phase (Li4V3O8). In-situ and operando energy dispersive X-ray diffraction (EDXRD) provided tomographic information to visualize the spatial location of the phase evolution within the LVO electrode while inside a sealed lithium ion battery.

Recently, gel polymer electrolytes (GPEs) have been drawn noteworthy attention for different applications, specifically, for supercapacitors. GPEs could become an excellent substitute to liquid electrolytes (LEs) for making flexible and more durable devices. The performance of two different electrolytes (GPEs and LEs) in multi-wall carbon nanotube based supercapacitors were investigated. In spite of significantly lower conductivity of GPEs than LEs, devices with the gel electrolyte presented a superior performance. More focused has been given in this work on demonstrating the performance of supercapacitors based on GPEs and LEs at different concentrations of the acids ranging from 1M to 3M. Both electrolytes have been characterized at room temperature by making supercapacitors and using cyclic voltammetry, charging-discharging, electrochemical impedance spectroscopy, and leakage tests. The experimental results showed that GPE devices had much better capacitances and resistances compare to the LE based devices. Moreover, the capacitances of all devices were increased proportionally with the increase in the concentration from 1M to 3M, and the resistances were increased inversely with the decreased of concentration. The promising results from the gel electrolytes is encouraging for further development of flexible and high capacitance energy storage devices.

Emerging applications require batteries to have both high energy and high power which are not necessarily compatible. The typical inverse relationship between power and energy in batteries is often due to the slow ion diffusion in electrode materials. While the optimization of current battery technology may be sufficient to fully address this issue, we present here that novel chemistry-focused strategies based on new fundamental understanding of materials may be applied to lead to the development of a new generation of batteries that store energy sufficiently and deliver it rapidly.