On the origin of the extra capacity at low potential in materials for Li batteries reacting through conversion reaction

The possibility of interfacial storage at low potential for electrode materials reacting through conversion reactions was evaluated. The amount of charge that could be stored through the proposed interfacial mechanism was estimated for a range of different materials and found to be much lower than those observed experimentally. Moreover, the slope of the potential decay and the influence of the current in the extent of stored capacity for experiments carried out in composite electrodes containing Co3O4 are not consistent with a capacitive-like mechanism. In summary, no evidence for capacitive storage could be found, our results being in agreement with the process taking place at low potential being solely related to electrolyte decomposition

Electrodeposition of arrays of Ru, Pt, and PtRu Alloy 1D metallic nanostructures

Arrays of Ru, Pt, and PtRu one dimensional 1D nanowires NWs and nanotubes NTs were prepared by electrodeposition through the porous structure of an anodic aluminum oxide AAO membrane. In each case, micrometer-long NW and NT were formed with an outer diameter of ca. 200 nm, close to the interior diameter of the porous AAO membrane. Arrays of NW and NT can be formed by varying the metallic salt concentration, the applied potential, and the conductivity of the electrolyte. The Ru and Pt deposition rates were measured in the various deposition conditions, using an electrochemical quartz crystal microbalance. The mechanisms responsible for the formation of Ru and Pt NW and NT are discussed based on the observed deposition rates and models found in the literature. Finally, it is shown that arrays of PtRu alloy NT and NW can be readily prepared and their compositions can be varied over the whole compositional range by changing the metallic salt concentration of the electrodeposition bath

Towards a calcium-based rechargeable battery

The development of a rechargeable battery technology using light electropositive metal anodes would result in a breakthrough in energy density1. For multivalent charge carriers (Mn+), the number of ions that must react to achieve a certain electrochemical capacity is diminished by two (n = 2) or three (n = 3) when compared with Li+ (ref. 2). Whereas proof of concept has been achieved for magnesium3, 4, 5, the electrodeposition of calcium has so far been thought to be impossible6 and research has been restricted to non-rechargeable systems7, 8, 9, 10. Here we demonstrate the feasibility of calcium plating at moderate temperatures using conventional organic electrolytes, such as those used for the Li-ion technology. The reversibility of the process on cycling has been ascertained and thus the results presented here constitute the first step towards the development of a new rechargeable battery technology using calcium anodes.Authors are grateful to F. Fauth for his assistance during data collection at the ALBA Synchrotron. The authors thank the Toyota Battery Research division at Higashi Fuji (M6) for their financial support.Peer reviewe

Achievements, Challenges, and Prospects of Calcium Batteries

This Review flows from past attempts to develop a (rechargeable) battery technology based on Ca via crucial breakthroughs to arrive at a comprehensive discussion of the current challenges at hand. The realization of a rechargeable Ca battery technology primarily requires identification and development of suitable electrodes and electrolytes, which is why we here cover the progress starting from the fundamental electrode/electrolyte requirements, concepts, materials, and compositions employed and finally a critical analysis of the state-of-the-art, allowing us to conclude with the particular roadblocks still existing. As for crucial breakthroughs, reversible plating and stripping of calcium at the metal-anode interface was achieved only recently and for very specific electrolyte formulations. Therefore, while much of the current research aims at finding suitable cathodes to achieve proof-of-concept for a full Ca battery, the spectrum of electrolytes researched is also expanded. Compatibility of cell components is essential, and to ensure this, proper characterization is needed, which requires design of a multitude of reliable experimental setups and sometimes methodology development beyond that of other next generation battery technologies. Finally, we conclude with recommendations for future strategies to make best use of the current advances in materials science combined with computational design, electrochemistry, and battery engineering, all to propel the Ca battery technology to reality and ultimately reach its full potential for energy storage

Towards standard electrolytes for sodium-ion batteries: physical properties, ion solvation and ion-pairing in alkyl carbonate solvents.

The currently emerging sodium-ion battery technology is in need of an optimized standard organic solvent electrolyte based on solid and directly comparable data. With this aim we have made a systematic study of "simple" electrolyte systems consisting of two sodium salts (NaTFSI and NaPF6) dissolved in three different alkyl carbonate solvents (EC, PC, DMC) within a wide range of salt concentrations and investigated: (i) their more macroscopic physico-chemical properties such as ionic conductivity, viscosity, thermal stability, and (ii) the molecular level properties such as ion-pairing and solvation. From this all electrolytes were found to have useful thermal operational windows and electrochemical stability windows, allowing for large scale energy storage technologies focused on load levelling or (to a less extent) electric vehicles, and ionic conductivities on par with analogous lithium-ion battery electrolytes, giving promise to also be power performant. Furthermore, at the molecular level the NaPF6-based electrolytes are more dissociated than the NaTFSI-based ones because of the higher ionic association strength of TFSI compared to PF6- while two different conformers of DMC participate in the Na+ first solvation shells - a Na+ affected conformational equilibrium and induced polarity of DMC. The non-negligible presence of DMC in the Na+ first solvation shells increases as a function of salt concentration. Overall, these results should both have a general impact on the design of more performant Na-conducting electrolytes and provide useful insight on the very details of the importance of DMC conformers in any cation solvation studies

Towards standard electrolytes for sodium-ion batteries: physical properties, ion solvation and ion-pairing in alkyl carbonate solvents

The currently emerging sodium-ion battery technology is in need of an optimized standard organic solvent electrolyte based on solid and directly comparable data. With this aim we have made a systematic study of "simple"electrolyte systems consisting of two sodium salts (NaTFSI and NaPF6) dissolved in three different alkyl carbonate solvents (EC, PC, DMC) within a wide range of salt concentrations and investigated: (i) their more macroscopic physico-chemical properties such as ionic conductivity, viscosity, thermal stability, and (ii) the molecular level properties such as ion-pairing and solvation. From this all electrolytes were found to have useful thermal operational windows and electrochemical stability windows, allowing for large scale energy storage technologies focused on load levelling or (to a less extent) electric vehicles, and ionic conductivities on par with analogous lithium-ion battery electrolytes, giving promise to also be power performant. Furthermore, at the molecular level the NaPF6-based electrolytes are more dissociated than the NaTFSI-based ones because of the higher ionic association strength of TFSI compared to PF6- while two different conformers of DMC participate in the Na+ first solvation shells-a Na+ affected conformational equilibrium and induced polarity of DMC. The non-negligible presence of DMC in the Na+ first solvation shells increases as a function of salt concentration. Overall, these results should both have a general impact on the design of more performant Na-conducting electrolytes and provide useful insight on the very details of the importance of DMC conformers in any cation solvation studies

Interfaces and Interphases in Ca and Mg Batteries

The development of high energy density battery technologies based on divalent metals as the negative electrode is very appealing. Ca and Mg are especially interesting choices due to their combination of low standard reduction potential and natural abundance. One particular problem stalling the technological development of these batteries is the low efficiency of plating/stripping at the negative electrode, which relates to several factors that have not yet been looked at systematically; the nature/concentration of the electrolyte, which determines the mass transport of electro-active species (cation complexes) toward the electrode; the possible presence of passivation layers, which may hinder ionic transport and hence limit electrodeposition; and the mechanisms behind the charge transfer leading to nucleation/growth of the metal. Different electrolytes are investigated for Mg and Ca, with the presence/absence of chlorides in the formulation playing a crucial role in the cation desolvation. From a R&D point-of-view, proper characterization alongside modeling is crucial to understand the phenomena determining the mechanisms of the plating/stripping processes. The state-of-the-art is here presented together with a short perspective on the influence of the cation solvation also on the positive electrode and finally an attempt to define guidelines for future research in the field

Electrode roughness dependent electrodeposition of sodium at the nanoscale

Na metal is an attractive anode material for rechargeable Na ion batteries, however, the dendritic growth of Na can cause serious safety issues. Along with modifications of solid-electrolyte interphase (SEI), engineering the electrode has been reported to be effective in suppressing Na dendritic growth, likely by reducing localized current density accumulation. However, fundamental understanding of Na growth at the nanoscale is still limited. Here, we report an in-situ study of Na electrodeposition in electrochemical liquid cells with the electrodes in different surface roughness, e.g., flat or sharp curvature. Real time observation using transmission electron microscopy (TEM) reveals the Na electrodeposition with remarkable details. Relatively large Na grains (in the micrometer scale) are achieved on the flat electrode surface. The local SEI thickness variations impact the growth rate, thus the morphology of individual grains. In contrast, small Na grains (in tens of nanometers) grow explosively on the electrode at the point with sharp curvature. The newly formed Na grains preferentially deposit at the base of existing grains close to the electrode. Further studies using continuum-based computational modeling suggest that the growth mode of an alkali metal (e.g. Na) is strongly influenced by the transport properties of SEI. Our direct observation of Na deposition in combination with the theoretical modeling provides insights for comprehensive understanding of electrode roughness and SEI effects on Na electrochemical deposition

On the strange case of divalent ions intercalation in V2O5

International audienceVanadium pentoxide has been investigated for multivalent ion battery technologies but the structural characterization of inserted phases is poor, and conflicting reports exist in the literature. This study presents a critical overview of controversial aspects related to Mg and Ca insertion in α-V2O5 under diverse conditions by combined electrochemical and ex-situ XRD experiments. Galvanostatic tests are carried out in dry and wet alkyl carbonate-based electrolytes at RT and 100 °C. The formation of protonated phases with negligible divalent ion content if any is evidenced by Rietveld refinements of the XRD data, unambiguously dismissing the presence of AV2O5 (A: Mg, Ca) as electrochemical reduction products. Furthermore, thermal instability of V2O5 at 100 °C in alkyl carbonate solvents is demonstrated by XRD and TEM analysis and the formation of an orthorhombic phase with increased a parameter, most likely due to degradation favored by both water and temperature, is observed for both Mg and Ca. In order to assess the feasibility of the reverse reaction, fully intercalated AV2O5 (A = Ca, Mg) phases were also prepared by solid state reaction and oxidation attempted both electrochemically and chemically without evidence of any significant amount of Mg2+ or Ca2+ extraction, further corroborating the sluggish diffusion kinetics of divalent cations in α-V2O5

A hybrid solid electrolyte for flexible solid-state sodium batteries

Development of Na-ion battery electrolyte with high-performance electrochemical properties and high safety is still challenging to achieve. In this study, we report on a NASICON (Na3Zr2Si2PO12)-based composite hybrid solid electrolyte (HSE) designed for use in a high safety solid-state sodium battery for the first time. The composite HSE design yields the required solid-state electrolyte properties for this application, including high ionic conductivity, a wide electrochemical window, and high thermal stability. The solid-state batteries of half-cell type exhibit an initial discharge capacity of 330 and 131 mA h g(-1) for a hard carbon anode and a NaFePO4 cathode at a 0.2C-rate of room temperature, respectively. Moreover, a pouch-type flexible solid-state full-cell comprising hard carbon/HSE/NaFePO4 exhibits a highly reversible electrochemical reaction, high specific capacity, and a good, stable cycle life with high flexibility.open0