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Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn

Solid-state electrolytes are attracting increasing interest for electrochemical energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liquid or gaseous active materials (for example, lithium–air, lithium–sulfur and lithium–bromine systems). A low-cost, safe, aqueous electrochemical energy storage concept with a ‘mediator-ion’ solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic conductivity, electrochemical stability and mechanical properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface. This Review details recent advances in battery chemistries and systems enabled by solid electrolytes, including all-solid-state lithium-ion, lithium–air, lithium–sulfur and lithium–bromine batteries, as well as an aqueous battery concept with a mediator-ion solid electrolyte.

Lithium battery chemistries enabled by solid-state electrolytes

Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries

The results of a systematic XPS study, under high controlled conditions, of different basic oxides of transition metals, alkali and alkaline-earth metals are presented; the XPS data of some hydroxides and peroxides are also reported. Variations of the O 1s binding energies are analysed and one point of interest is the large
 binding energy scale obtained for O 1s peaks all associated with a ‘‘2−
’’ formal charge. Through extended
 Huckel theory-tight binding (EHT-TB) calculations, attempts are made to rationalize the observed variations.
 The results illustrate
 the significant
 differences
 between real
 charges on oxygen atoms in transition metal and alkaline-earth oxides.

Systematic XPS studies of metal oxides, hydroxides and peroxides

A review of conduction phenomena in Li-ion batteries

Etude comparee de la conductivite ionique du lithium dans les halogenoborates vitreux

Investigations of structure and transport in lithium and silver borophosphate glasses

Characterisation of r.f. sputtered tungsten disulfide and oxysulfide thin films

Different technologies allow one to obtain battery materials in the form of thin films. Physical methods, i.e. evaporation or sputtering, and chemical methods, i.e. chemical vapour deposition, are mainly used. Thin film microbatteries have been studied for 30 years. The first reason for the use of thin films in battery technology was the low ionic conductivity of the solid electrolyte used; reducing its thickness provided a relatively low internal resistance to the cells. After this first step concerning mainly the electrolyte, thin film technologies were applied to all the battery elements. Following the miniaturization of electronic devices, thin film solid state batteries are receiving some new attention, motivated by the desire for a battery that can be fully integrated with microcircuits. Lithium microbatteries have been the most studied; while some of them are the replica of “classical” batteries using a liquid elettrolyte, e.g. the Li/TiS 2 system, others use new materials. Very interesting results have been obtained. Because of the very high conductivity of silver conducting electrolytes, silver microbatteries have also been extensively studied and significant results obtained with a primary cell design. Other systems using fluoride or copper as ionic conductor have also been considered; they are characterized by a low available voltage.

Solid state microbatteries

This films of titanium oxysulphides have been obtained by radio-frequency sputtering and used as positive electrodes in all-solid-state microbatteries with ternary sputtered oxide glass (B 2 O 3 -Li 2 O-Li 2 SO 4 ) as the electrolyte and evaporated lithium as the negative electrode. More than 50 cycles were readily obtained for current densities up to 62 μA cm−2. The electrochemical properties have been determined. The positive electrode has been characterized by several techniques: Auger spectroscopy, Rutherford backscattering and secondary ion mass spectrometry.

Alain Levasseur

Papers

Etude comparee de la conductivite ionique du lithium dans les halogenoborates vitreux

Investigations of structure and transport in lithium and silver borophosphate glasses

Characterisation of r.f. sputtered tungsten disulfide and oxysulfide thin films

Solid state microbatteries

New positive-electrode materials for lithium thin film secondary batteries☆