Structural and electrochemical insights into novel Wadsley Roth Nb7Ti1.5Mo1.5O25 and Ta7Ti1.5Mo1.5O25 anodes for Li-ion battery application.

Niobium based anodes are gaining increasing popularity for application in high-power lithium-ion batteries, due to their high theoretical capacities, inherent safety at high current densities, and long-term stability. Here, we report the discovery and characterisation of a new Wadsley Roth niobate system, Nb7Ti1.5Mo1.5O25, showing that it is isostructural with known systems: Nb9PO25 and Nb9VO25. To evaluate the material's electrochemical performance, including performance at high current densities (for potential high power applications), and long-term stability, Li half-coin cells were prepared. The material showed an initial capacity of 268(9) mA h g-1 at 0.01 A g-1 (voltage range of 2.5-1.0 V). However, in subsequent cycles, some of this initial capacity is lost, which is attributed to Li trapping associated with the presence of reducible MoO4 units, similar to the situation observed for isostructural Nb9VO25. After this initial irreversible capacity loss, the material showed good performance at high current density rates, such that at 2 A g-1 and 4 A g-1 respective capacities of 132(10) mA h g-1 and 115(14) mA g-1 were delivered. Moreover, the material showed respectable capacity retention (97%) after being cycled for 100 cycles at 0.2 A g-1. In order to identify the different Nb, Ti, Mo redox couples involved in this system, a Ta analogue was also synthesized (Ta7Ti1.5Mo1.5O25) and the electrochemical performance for this phase is also reported. This phase shows a lower initial capacity at 0.01 A g-1 (140(3) mA h g-1) than the Nb analogue in the same voltage range, which can be increased (225 mA h g-1) if a lower cutoff voltage (0.5 V) is applied. The capacity retention for this Ta system after 100 cycles at 0.2 A g-1 is similar to the Nb analogue (97%). Further work has explored whether the Nb-Ti-Mo contents could be varied, and these results showed that single phase Nb10-2xTixMoxO25 samples could be prepared for 1.5 ≤ x ≤ 1.75, and electrochemical testing results for the x = 1.75 endmember are also reported. Overall, this research highlights the synthesis and electrochemical characterisation of two new Wadsley Roth phases, and further highlights the challenges associated with the presence of reducible cations in tetrahedral sites in such structures with respect to minimising initial irreversible capacity loss.

Evaluation of Ga0.2Li6.4Nd3Zr2O12 garnets: exploiting dopant instability to create a mixed conductive interface to reduce interfacial resistance for all solid state batteries.

The next major leap in energy storage is thought to arise from a practical implementation of all solid-state batteries, which remain largely confined to the small scale due to issues in manufacturing and mechanical stability. Lithium batteries are amongst the most sought after, for the high expected energy density and improved safety characteristics, however the challenge of finding a suitable solid-state electrolyte remains. Lithium rich garnets are prime contenders as electrolytes, owing to their high ionic conductivity (>0.1 mS cm-1), wide electrochemical window (0-6 V) and stability with Li metal. However, the high Young's modulus of these materials, poor wetting of Li metal and rapid formation of Li2CO3 passivating layers tends to give a detrimentally large resistance at the solid-solid interface, limiting their application in solid state batteries. Most studies have focused on La based systems, with very little work on other lanthanides. Here we report a study of the Nd based garnet Ga0.2Li6.4Nd3Zr2O12, illustrating substantial differences in the interfacial behaviour. This garnet shows very low interfacial resistance attributed to dopant exsolution which, when combined with moderate heating (175 °C, 1 h) with Li metal, we suggest forms Ga-Li eutectics, which significantly reduces the resistance at the Li/garnet interface to as low as 67 Ω cm2 (much lower than equivalent La based systems). The material also shows intrinsically high density (93%) and good conductivity (≥0.2 mS cm-1) via conventional furnaces in air. It is suggested these garnets are particularly well suited to provide a mixed conductive interface (in combination with other garnets) which could enable future solid-state batteries.

Raman spectroscopy insights into the α- and δ-phases of formamidinium lead iodide (FAPbI3).

Solar perovskites have received phenomenal attention and success over the past decade, due to their high power conversion efficiencies (PCE), ease of fabrication and low cost which has enabled the prospect of them being a real commercial contender to the traditional silicon technology. In one of the several developments on the archetypal MAPbI3 perovskite absorber layer, FAPbI3 was found to obtain a higher PCE, likely due to its more optimum band gap, with doping strategies focusing on the inclusion of MA+/Cs+ cations to avoid the unfavourable phase transformation to a photoinactive phase. To better understand the phase change from the photoactive cubic (Pm3[combining macron]m) black (α) phase to the unwanted photoinactive (P63/mmc) yellow (δ) phase, we make use of variable temperature Raman spectroscopy to probe the molecular species and its relationship to the inorganic framework. We show for the first time there to be no Raman active modes for the α phase up to 4000 cm-1, which can be correlated to the Pm3[combining macron]m cubic symmetry of that phase. Our detailed studies suggest that previous reports of the observation of Raman peaks for this phase are likely associated with degradation reactions from the localised laser exposure and the formation of Raman active lead oxide. In addition, we have identified water as a contributing factor to the transformation, and observed a corresponding signal in the Raman spectra, although confirmation of its exact role still remains inconclusive.

Water based synthesis of highly conductive GaxLi7-3xLa3Hf2O12 garnets with comparable critical current density to analogous GaxLi7-3xLa3Zr2O12 systems.

Next generation lithium ion batteries are envisaged as those which feature an all solid-state architecture. This will enable the higher energy density storage required to meet the demands of modern society, especially for the growing electric vehicle market. Solid state batteries have, however, proved troublesome to implement commercially due to the lack of a suitable solid-state electrolyte, which needs to be highly conductive, have a low interfacial resistance and a suitably wide electrochemical stability window. Garnet materials are potential contenders for these batteries, demonstrating many of the desired properties, although there remain challenges to overcome. Here we report a facile synthesis of Li7La3Hf2O12 and Ga/AlxLi7-3xLa3Hf2O12 garnets, with the synthesis of Ga0.2Li6.4La3Hf2O12 requiring only dissolution of precursors in water and heating to 700 °C. Ga0.2Li6.4La3Hf2O12 was shown to display a high room temperature conductivity (0.373 mS cm-1 at 28 °C). Moreover, in Li|garnet|Li cells, we observed a comparable critical current density compared to Ga0.2Lai6.4La3Zr2O12, despite a lower density and higher area specific resistance compared to literature values, suggesting Hf systems may be further engineered to deliver additional improvements for use in future solid state batteries.

Carbon dioxide and water incorporation mechanisms in SrFeO3-δ phases: a computational study.

With a higher propensity for low temperature synthesis routes along with a move toward lower solid oxide fuel cell operating temperatures, water and carbon dioxide incorporation in strontium ferrite is of importance. Despite this, the mechanisms are not well understood. In this work, classical-potential-based computational techniques are used to determine the favourability of water and CO2 incorporation mechanisms in both SrFeO3-δ and SrFeO2.5. Our studies suggest that intrinsic Frenkel and Schottky type defects are unlikely to form, but that water and carbon dioxide incorporation are favourable in both phases. Water incorporation is likely for both the cubic and brownmillerite phases, with hydroxyl ions preferring to sit on octahedral oxygen sites in both structures, causing slight tilting of the shared octahedra. Interstitial hydroxyl ions are only likely for the brownmillerite phase, where the hydroxyl ions are most stable between adjacent FeO4 tetrahedral chains. Carbon dioxide incorporation via carbonate defects is most favourable when a carbonate molecule exists on an iron site, preferring the iron site with lower oxygen coordination. This involves formation of multiple oxygen vacancies surrounding the iron site, and thus we conclude that carbonate can trap oxygen vacancies.

The Building Blocks of Battery Technology: Using Modified Tower Block Game Sets to Explain and Aid the Understanding of Rechargeable Li-Ion Batteries.

While Li-ion batteries are abundant in everyday life from smart phones to electric vehicles, there are a lack of educational resources that can explain their operation, particularly their rechargeable nature. It is also important that any such resource can be understood by a wide range of age groups and backgrounds. To this end, we describe how modified tower block games sets, such as Jenga, can be used to explain the operation of Li-ion batteries. The sets can also be utilized to explain more advanced topics such as battery degradation and challenges with charging these batteries at high rates. In order to make the resource more inclusive, we also illustrate modifications to prepare tactile tower block sets, so that the activity is also suitable for blind and partially sighted students. Feedback from a range of groups supports the conclusion that the tower block sets are a useful tool to explain Li-ion battery concepts.

Evaluation of the effect of site substitution of Pr doping in the lithium garnet system Li5La3Nb2O12.

Li ion conducting garnets have been attracting considerable interest for use as the electrolyte in all solid-state batteries, due to their high ionic conductivity and wide electrochemical stability window. Consequently, there have been a number of doping studies aimed at optimising the conductivity, focusing on both doping in Li7La3Zr2O12 and Li5La3(Nb/Ta)2O12 systems. In this paper, we report a detailed study of Pr doping in Li5La3Nb2O12, and show that this is a rare example of an ambi-site dopant, being able to be doped onto either the La or Nb site. Interestingly the resultant Pr oxidation state is determined by the site substitution, with oxidation states of 3+ for the La site, and 4+ for the Nb site. While the conductivity is essentially unchanged for the La site substitution, Pr4+ substitution on the Nb site leads to a large increase in the conductivity associated with the increase in Li content (Li5+xLa3Nb2-xPrxO12) up to 0.56 mS cm-1 (at 50 °C) for x = 0.8. Overall, this work highlights the flexibility of these garnet materials to doping, and suggests that further consideration of site substitution be considered for other dopants.

Designing a facile low cost synthesis strategy for the Na-V-S-O systems, NaV(SO4)2, Na3V(SO4)3 and Na2VO(SO4)2.

Alkali metal transition metal sulfates have attracted considerable interest as potential electrodes for Na ion battery materials. While there has been significant research on Fe based systems, research on V based systems has been lacking, apart from a recent report on Na2VO(SO4)2. This can be related to the complex synthetic routes previously reported to make sodium vanadium sulfate systems. In this paper, we report a simple route towards the synthesis of three such sodium vanadium sulfate systems, NaV(SO4)2, Na2VO(SO4)2, and Na3V(SO4)3. We analyse the resulting products through X-ray diffraction and Raman spectroscopy to highlight the formation of high quality samples via this simple solution route, with subsequent low temperature (<400 °C) heat treatment. This facile new route will allow these materials to be considered for future applications rather than as simply chemical curiosities.

Effect of tri- and tetravalent metal doping on the electrochemical properties of lanthanum tungstate proton conductors.

Rare-earth tungstates (La(28-y)W(4+y)O(54+δ)□(2-δ)) have attracted attention recently because of their relatively high proton-electron conductivity and high stability in a CO2 environment. Since doping on the tungsten-site may increase the conductivity, a new series of compounds with composition La(5.5)W(1-x)M(x)O(11.25-δ) (M = Al, Ti and Zr; x = 0, 0.05 and 0.10) have been investigated. The crystal structure of these materials has been studied using X-ray and time-of-flight neutron powder diffraction by Rietveld analysis. The concentration of oxygen vacancies for hydration in the structure has been indirectly determined by thermogravimetric analysis, and the total conductivity in several pO2, pH2O and pD2O atmospheres has been studied by impedance spectroscopy. An increase in the conductivity is observed, ranging from 4.1 mS cm(-1) for the undoped sample to 9.2 mS cm(-1) for La(5.5)W(0.9)Ti(0.1)O(11.25-δ), in wet N2 at 800 °C.

Oxyanions in perovskites: from superconductors to solid oxide fuel cells.

In this article we review work on oxyanion (carbonate, borate, nitrate, phosphate, sulphate, silicate) doping in perovskite materials beginning with early work on doping studies in superconducting cuprates, and extending to more recent work on doping into perovskite-type solid oxide fuel cell materials. In this doping strategy, the central atom of the oxyanion group occupies the perovskite B cation site, with the associated oxide ions filling 3 (carbonate, nitrate, borate) or 4 (phosphate, sulphate, silicate) of the available 6 anion sites around this site, albeit displaced so as to achieve the required geometry for the oxyanion. We highlight the potential of this doping strategy to prepare new systems, stabilize phases that cannot be prepared under ambient pressure conditions, and lead to modifications to the electronic and ionic conductivity. We also highlight the need for further work in this area, in particular to evaluate the carbonate content of perovskite phases in general.

Effect of Ga incorporation on the structure and Li ion conductivity of La3Zr2Li7O12.

In this paper we examine the effect of Ga doping on the structure and conductivity of the high Li ion content garnet-related system, La(3)Zr(2)Li(7)O(12). Without Ga doping, La(3)Zr(2)Li(7)O(12) is tetragonal and has low Li ion conductivity. The introduction of Ga leads to a change to a cubic unit cell, and a large enhancement in the conductivity. Prior structural studies of La(3)Zr(2)Li(7)O(12) have shown the presence of both tetrahedral and distorted octahedral sites for Li, and the low conductivity can be explained by the ordered nature of the Li distribution. The present structural study of La(3)Zr(2)Ga(0.5)Li(5.5)O(12) shows that Ga substitutes onto the tetrahedral site. Despite the presence of non-mobile Ga(3+) on the Li sites, the conductivity is enhanced as a result of the introduction of vacancies in the Li sites, and consequent disorder on the Li sublattice. Further work has suggested that over time in air, there is some H(+)/Li(+) exchange, and consequently some variation in the conductivity.

Synthesis and characterization of proton conducting oxyanion doped Ba2Sc2O5.

In this paper we report the successful synthesis of the cubic oxyanion containing perovskites, Ba(2)Sc(2-x)P(x)O(5+x) (x = 0.4, 0.5), with the samples analysed through a combination of X-ray diffraction, NMR, TGA, Raman spectroscopy and conductivity measurements. Conductivity measurements indicate a p-type contribution to the conductivity in oxidizing conditions at elevated temperatures, with evidence for proton conduction in wet atmospheres. For the latter, bulk conductivities of 5.9 × 10(-3) and 1.3 × 10(-3) S cm(-1) at 500 °C were obtained for x = 0.4 and 0.5 respectively, comparable to other perovskite proton conductors, while the stability towards CO(2) containing atmospheres was improved compared to BaCeO(3) based systems. Related Si doped systems have also been prepared, although in this case small Ba(2)SiO(4) impurities are observed. We also provide evidence to suggest that "undoped" Ba(2)Sc(2)O(5) contains carbonate groups, which accounts for its thermal instability.

Apatite germanates doped with tungsten: synthesis, structure, and conductivity.

High oxygen content apatite germanates, La(10)Ge(6-x)W(x)O(27+x), have been prepared by doping on the Ge site with W. In addition to increasing the oxygen content, this doping strategy is shown to result in stabilisation of the hexagonal lattice, and yield high conductivities. Structural studies of La(10)Ge(5.5)W(0.5)O(27.5) show that the interstitial oxygen sites are associated to a different degree with the Ge/WO(4) tetrahedra, leading to five coordinate Ge/W and significant disorder for the oxygen sites associated with these units. Raman spectroscopy studies suggest that in the case of the WO(5) units, the interstitial oxygen is more tightly bonded and therefore not as mobile as in the case of the GeO(5) units, thus not contributing significantly to the conduction process.

Cation ordering in Li containing garnets: synthesis and structural characterisation of the tetragonal system, Li7La3Sn2O12.

In this paper we report synthesis, conductivity and structural data for the novel tetragonal garnet-related system, Li7La3Sn2O12. Neutron diffraction data shows that the tetragonal distortion is related to ordering of Li in three sites within the structure to ensure no short Li-Li interactions. Consistent with the ordered nature of the Li ions, the conductivity is low, with a high activation energy. The results are relevant to related highly conducting cubic garnets, Li5+xLn3-xAxM2O12 (Ln=rare earth, A=alkaline earth; M=Nb, Ta, Sb), showing how a high Li content can be accommodated by Li ordering within the garnet structure, supporting previous suggestions by Cussen for the cubic garnets, who proposed the presence of local ordering/clustering of Li in tetrahedral and "octahedral" sites to limit unfavourable short Li-Li interactions.

Effect of oxygen content on the 29Si NMR, Raman spectra and oxide ion conductivity of the apatite series, La8+xSr2-x(SiO4)6O2+x/2.

29Si NMR data have been recorded for the apatite series La8+xSr2-x(SiO4)6O2+x/2 (0 < or = x < or = 1.0). For x = 0, a single NMR peak is observed at a chemical shift of approximately -77 ppm, while as the La : Sr ratio and hence interstitial oxygen content is increased, a second peak at a chemical shift of approximately -80 ppm is observed, which has been attributed to silicate groups neighbouring interstitial oxide ions. An increase in the intensity of this second peak is observed with increasing x, consistent with an increase in interstitial oxide ion content, and the data are used to estimate the level of interstitial oxide ions, and hence Frenkel-type disorder in these materials. The increase in second 29Si NMR peak intensity/interstitial oxide ion content is also shown to correlate with an increase in conductivity. The effect of interstitial oxygen content can also be studied by means of Raman spectroscopy, with a new mode at 360 cm(-1) appearing for samples with x > 0 in the symmetric bending mode energy region of the SiO4 group. The intensity of this mode increases with increasing oxygen content, yielding results comparable to those from the NMR studies, showing the complementarities of the two techniques.

Neutron diffraction and atomistic simulation studies of Mg doped apatite-type oxide ion conductors.

In this paper, detailed studies of the effect of Mg doping in the apatite-type oxide ion conductor La9.33Si6O26 are reported. Mg is confirmed as an ambisite dopant, capable of substituting for both La and Si, depending on the starting composition. A large enhancement in the conductivity is observed for Si site substitution, with a reduction for substitution on the La site. Neutron powder diffraction studies show that in agreement with cation size expectations, an enlargement of the unit cell is observed on Mg substitution for Si, with a corresponding increase in the size of the tetrahedral sites. For Mg substitution on the La site, a contraction of the unit cell is observed, and the neutron diffraction results indicate that there is preferential occupancy of Mg on the La2 (1/3, 2/3, approximately 0.5) site. Atomistic simulation studies show significant local structural changes affecting the oxide ion channels in both cases. Mg doping on the Si site leads to a local expansion of the channels, while doping on the La site results in a large displacement of the silicate O4 site, such that it encroaches the oxide ion channels. The observed differences in conductivities are discussed with respect to these observations.

Doping strategies to optimise the oxide ion conductivity in apatite-type ionic conductors.

The apatite-type phases, La(9.33+x)(Si/Ge)(6)O(26+3x/2), have recently been attracting considerable interest as potential electrolytes for solid oxide fuel cells. In this paper we report results from a range of doping studies in the Si based systems, aimed at determining the key features required for the optimisation of the conductivities. Systems examined have included alkaline earth doping on the rare earth site, and P, B, Ga, V doping on the Si site. By suitable doping strategies, factors such as the level of cation vacancies and oxygen excess have been investigated. The results show that the oxide ion conductivities of these apatite systems are maximised by the incorporation of either oxygen excess or cation vacancies, with the former producing the best oxide ion conductors. In terms of samples containing cation vacancies, conductivities are enhanced by doping lower valent ions, Ga, B, on the Si site. The presence of higher valent ions on these sites, e.g. P, appears to inhibit the incorporation of excess oxygen within the channels, and so limits the maximum conductivity that can be obtained. Overall the results suggest that the tetrahedral sites play a key role in the conduction properties of these materials, supporting recent modelling studies, which have suggested that these tetrahedra aid in the motion of the oxide ions down the conduction channels by co-operative displacements.

Development of apatite-type oxide ion conductors.

Research into materials displaying oxide ion conductivity is attracting considerable attention due to their potential technological applications in devices such as Solid Oxide Fuel Cells. In this paper, recent work on apatite-type oxide ion conductors is reviewed, showing that a wide range of cation substitutions are possible, due to the flexibility of the apatite structure in accommodating a range of ion sizes. The conductivity studies on these doped samples show that to achieve high oxide ion conduction, non-stoichiometry in terms of cation vacancies and/or oxygen excess is required, with the latter resulting in the highest conductivities. In contrast to most common oxide ion conductors, e.g. perovskite and fluorite in which oxide ion conduction proceeds via oxygen vacancies, the research on these apatite systems suggests that the conductivity involves interstitial oxide ions. With further optimization of these materials, particularly in terms of the Ge-containing systems, significant improvements in conductivity are likely, leading to the very real possibility of the application of apatite-type electrolytes in fuel cell and other applications.