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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

The disclosure herein relates to a lithium ion conducting electrolyte. This electrolytic material has improved ionic conductivity. The material disclosed herein is an amorphous compound of the formula Li x SM w O y N z wherein x is between approximately 0.5 and 3, y is between 1 and 6, z is between 0.1 and 1, w is less than 0.3 and M is an element selected from B, Ge, Si, P, As, Cl, Br, I, and combinations thereof. The material can be prepared in the form of a thin film. The electrolyte material can be used in microbatteries and elctronic systems.

Lithium ion conducting lithium sulphur oxynitride thin film, and a process for the preparation thereof

Several WOySz tungsten oxysulphide thin films were tested as positive electrodes for lithium microbatteries. The amorphous WO1.05S2 thin film was found very promising. A capacity decrease occurred during the first few cycles, after which the films were able to intercalate reversibly up to 11 lithium ion per formula unit under high regime (75 μA/cm2). They were tested for 250 charge-discharge cycles, between 30 V and 1.2 V. X-ray photoelectron spectroscopy measurements were performed on different compounds in both intercalated (Li1WO1.05S2, Li2.7WO1.05S2 and Li3.8WO1.05S2) and partially deintercalated (Li1WO1.05S2) states in order to understand the redox processes occurring during the first dischargecharge cycle. The analysis of both the W4f and the S2p peaks has shown that the redox processes involve not only the tungsten atoms but also sulphur atoms. At the beginning of the intercalation, W6+ was first partially reduced into W5+, and then into W4+, but the important stage was the reduction of W4+ into W0. In W0, the electron binding energy was very close to that of metallic tungsten. At the same time, S
 2
 2-
 ions were partially reduced into S2- ions. But only the reduction process of tungsten atoms appeared to be totally reversible.

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Electrochemical properties of tungsten oxysulphide thin films as positive electrodes for lithium microbatteries

ESR of X-ray irradiated boracites

The core and valence electronic binding energies of vitreous and crystalline compounds in the B 2 S 3 -Li 2 S system have been investigated by XPS and analysed using theoretical calculations. Analysis of the XPS core S2p peaks led to the distinction of various types of sulphur atoms. One criterion is their coordination to boron: either triple, double (bridging sulphurs: 'bS'), or single (nonbridging sulphurs: 'nbS'). In addition, sulphur atoms bound to 4-coordinated boron have been found more negatively charged than the same bound to 3-coordinated boron. The effect of charge delocalisation within boron sulphur rings has also been evidenced. For some compounds the data analysis has been supported by ab initio cluster calculations. For crystalline Li3BS3 the XPS valence spectrum has been interpreted on the basis of TB-EHT calculations and compared to that of the corresponding glass.

XPS analyses of B2S3-Li2S glasses. Experimental and theoretical study

Solid state (Li/B 2 S 3 -Li 2 S-LiI glass/interaction compound) cells were constructed using an isostatic pressing process. Their discharge is compared with that of corresponding liquid electrolyte cells (LiClO 4 -PC). V 6 O 13 , TiS 2 , LiW 3 O 9 F and a-MoS 3 were utilized, showing that the interacalation compound must present multi-directional diffusion for lithium as well as no volume change upon intercalation in order to achieve comparable discharge characteristics for solid and liquid electrolyte cells.

Alain Levasseur

Papers

Lithium ion conducting lithium sulphur oxynitride thin film, and a process for the preparation thereof

Electrochemical properties of tungsten oxysulphide thin films as positive electrodes for lithium microbatteries

ESR of X-ray irradiated boracites

XPS analyses of B2S3-Li2S glasses. Experimental and theoretical study

On the behavior of interactlation compounds in solid state batteries