Titanium dioxide is one of the most intensely studied oxides due to its interesting electrochemical and photocatalytic properties and it is widely applied, for example in photocatalysis, electrochemical energy storage, in white pigments, as support in catalysis, etc. Common synthesis methods of titanium dioxide typically require a high temperature step to crystallize the amorphous material into one of the polymorphs of titania, e.g. anatase, brookite and rutile, thus resulting in larger particles and mostly non-porous materials. Only recently, low temperature solution-based protocols gave access to crystalline titania with higher degree of control over the formed polymorph and its intra- or interparticle porosity. The present work critically reviews the formation of crystalline nanoscale titania particles via solution-based approaches without thermal treatment, with special focus on the resulting polymorphs, crystal morphology, surface area, and particle dimensions. Special emphasis is given to sol-gel processes via glycolated precursor molecules as well as the miniemulsion technique. The functional properties of these materials and the differences to chemically identical, non-porous materials are illustrated using heterogeneous catalysis and electrochemical energy storage (battery materials) as example.

In this paper we examine the mechanism of Na insertion and extraction in the FePO 4 -NaFePO 4 system. Chemical preparation of the intermediate Na 1Àx FePO 4 phase has revealed the existence of a range of stable compositions with different Na + /vacancy arrangements. The mechano-chemical aspects of the charge and discharge reactions are also discussed.

Lithium has been inserted into the spinel Li 4 Ti 5 O 12 by both chemical and electrochemical methods. The cation distribution in the lithiated phases has been analyzed by 6,7 Li NMR, Raman spectroscopy, and X-ray diffraction, and the distribution in the chemically inserted compound has been analyzed additionally by neutron diffraction. A refinement of structural parameters has been carried out by applying the Rietveld method to the neutron diffraction pattern. It is shown that the two insertion methods are based on different mechanisms. Chemically inserted lithium ions are trapped in the (48f) sites of the spinel structure from which they cannot be extracted by electrochemical means. In contrast to the electrochemical Li-insertion, which is accompanied by a spinel to rocksalt phase transition, no such structural change is found for chemical insertion. The consequences of the two different mechanisms for the reversibility of the insertion process are discussed.

Different samples of the sodium-vanadium fluorophosphate cathodic materials have been synthesized via the hydrothermal method, varying the type and content of carbon used in the synthesis. Structural characterization of the composites was performed by powder X-ray diffraction. Magnetic susceptibility measurements and EPR (Electron Paramagnetic Resonance) polycrystalline spectra indicate that some of the samples exhibit V 3+ /V 4+ mixed valence, with the general formula Na 3 V 2 O 2x (PO 4 ) 2 F 3À2x where 0 # x < 1. The morphology of the materials was analyzed by Transmission Electron Microscopy (TEM). A correlation between the type and content of carbon with the electrochemical behavior of the different samples was established. Electrochemical measurements conducted using Swagelok-type cells showed two voltage plateaux at 3.6 and 4.1 V vs. Na/Na + . The best performing sample, which comprised a moderate percentage of electrochemical grade carbon as additive, exhibited specific capacity values of about 100 mA h g À1 at 1C (z80% of theoretical specific capacity). Cyclability tests at 1C proved good reversibility of the material that maintained 98% of initial specific capacity for 30 cycles.

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The cycling performance fade of LFP-based Li-ion cylindrical batteries is evaluated under maximum cycling voltage amplitude. Diagnostic evaluation of the ageing mechanisms included in-situ electrochemical measurements and ex-situ destructive physico-chemical and electrochemical analyses of cell components. SEM, EDS, XRD and electrochemical measurements of harvested electrodes confirmed that the primary cell performance degradation modes are loss of active lithium inventory (LLI) and loss of active material (LAM) related to graphite electrode. Ageing phenomena were associated with the progressive decomposition of the electrolyte. Cell capacity loss was concluded to be dominated by SEI layer growth, which also led to a sharp power loss together with localised lithium plating on the negative electrode surface upon prolonged cycling. Graphite surface was polymerised and inactivated in localised central parts of the jelly-roll, leading to large cavities as a result of metallic lithium and electrolyte reactions. No degradation of the structure or performance of the LFP positive electrode was detected. In this paper, ageing processes are examined in the overall context of cell performance fade during accelerated cycling operation.

A mixed-valence V3+/V4+ composite material belonging to the Na3V2O2x (PO4)2F3–2x /C family is synthesized and the electrochemical Na extraction/insertion mechanism is determined using a combination of high-resolution synchrotron X-ray diffraction (XRD) data, X-ray absorption spectroscopy (XAS), 23Na and 19F solid state nuclear magnetic resonance (NMR), double titration (for the elucidation of the vanadium oxidation state), and electrochemical measurements. The vanadium oxidation state is found to be +3.8 for the as-prepared sample. Detailed analysis of the cathode structural evolution illustrated that the V4+/V5+ couple is active in this compound during electrochemical cycling between 2.8 V and 4.3 V. This study demonstrates how the sodium-ion extraction and insertion pathways in cathode materials can be followed (and verified) using several experimental techniques, especially when multiple potential oxidation states are present in the parent compound.

Ambient temperature sodium-ion batteries are emerging as an exciting alternative to commercially dominant lithium-ion batteries for larger scale stationary applications. In order to realize such a sodium-ion battery, electrodes need to be developed, understood, and improved. Here, Na 3 V 2 O 2 (PO 4 ) 2 F is investigated from the perspective of sodium. Reaction mechanisms for this cathode during battery function include the following: a region comprising at least three phases with subtly varying sodium compositions that transform via two two-phase reaction mechanisms, which appears at the lower potential plateau-like region during both charge and discharge; an extended solid solution region for majority of the cycling process, including most of the higher potential plateau; and a second two-phase region near the highest charge state during charge and between the first and second plateau-like regions during discharge. Notably, the distinct asymmetry in the reaction mechanism, lattice, and volume evolution on charge relative to discharge manifests an interesting question: Is such an asymmetry beneficial for this cathode? These reaction mechanisms are inherently related to sodium evolution, which shows complex behavior between the two sodium crystallographic sites in this compound that in turn mediate the lattice and reaction evolution. Thus, this work relates atomiclevel sodium perturbations directly with electrochemical cycling.