Accelerating Cathode Material Discovery through Ab Initio Random Structure Searching

The choice of cathode material in Li-ion batteries underpins their overall performance. Discovering new cathode materials is a slow process, and all major commercial cathode materials are still based on those identified in the 1990s. Discovery of materials using high-throughput calculations has attracted great research interest; however, reliance on databases of existing materials begs the question of whether these approaches are applicable for finding truly novel materials. In this work, we demonstrate that ab initio random structure searching (AIRSS), a first-principles structure prediction method that does not rely on any pre-existing data, can locate low energy structures of complex cathode materials efficiently based only on chemical composition. We use AIRSS to explore three Fe-containing polyanion compounds as low-cost cathodes. Using known quaternary LiFePO4 and quinary LiFeSO4F cathodes as examples, we easily reproduce the known polymorphs, in addition to predicting other, hitherto unknown, low energy polymorphs and even finding a new polymorph of LiFeSO4F that is more stable than the known ones. We then explore the phase space for Fe-containing fluoroxalates, predicting a range of redox-active phases that are yet to be experimentally synthesized, demonstrating the suitability of AIRSS as a tool for accelerating the discovery of novel cathode materials

Prognostic value of PDCD-1 and CTLA-4 in ovarian cancer patients

Therapeutic effectiveness of treatments for ovarian cancer is not optimal. PDCD-1 and CTLA-4 offers the potential as a prognostic marker in addition to being a target for therapy. To assess the prognostic roles of PDCD-1 and CTLA-4 Gene in ovarian cancer, we utilized the Kaplan Meier plotter, a biomarker assessment tool with large quantities of data. The relationship between PDCD-1 and overall survival (OS) as well as CTLA-4 and OS were presented using Hazard Ratio, 95% CI and logrank P value. Then gene expression level was compared using H-Test and U test. The results were as follows: PDCD-1 and CTLA-4 gene expressions among 1582 ovarian cancer patients were shown with median gene expression value as the cut-off. Expression of PDCD-1 and CTLA-4 did not differ with regard to stages and P53 gene mutation. But the expression of CTLA-4 was higher in endometrioid than in serous cancer patients. Different grades of both PDCD-1 and CTLA-4 had different mean values. Higher expression of the PDCD-1 was not significantly correlated with better OS with HR 0.88 (95% CI: 0.77-1.01, P=0.061) but higher CTLA-4 was associated with better survival with HR 0.84 (95% CI: 0.73-0.96, P=0.0099) on the transcriptome level. In conclusion, lower expression of CTLA-4, but not PDCD-1 predicts worse survival

Ab initio random structure searching for battery cathode materials

Cathodes are critical components of rechargeable batteries. Conventionally, the search for cathode materials relies on experimental trial-and-error and a traversing of existing computational/experimental databases. While these methods have led to the discovery of several commercially viable cathode materials, the chemical space explored so far is limited and many phases will have been overlooked, in particular, those that are metastable. We describe a computational framework for battery cathode exploration based on ab initio random structure searching (AIRSS), an approach that samples local minima on the potential energy surface to identify new crystal structures. We show that by delimiting the search space using a number of constraints, including chemically aware minimum interatomic separations, cell volumes, and space group symmetries, AIRSS can efficiently predict both thermodynamically stable and metastable cathode materials. Specifically, we investigate LiCoO2, LiFePO4, and LixCuyFz to demonstrate the efficiency of the method by rediscovering the known crystal structures of these cathode materials. The effect of parameters, such as minimum separations and symmetries, on the efficiency of the sampling is discussed in detail. The adaptation of the minimum interatomic distances on a species-pair basis, from low-energy optimized structures to efficiently capture the local coordination environment of atoms, is explored. A family of novel cathode materials based on the transition-metal oxalates is proposed. They demonstrate superb energy density, oxygen-redox stability, and lithium diffusion properties. This article serves both as an introduction to the computational framework and as a guide to battery cathode material discovery using AIRSS

Determining interface structures in vertically aligned nanocomposite films

Vertically aligned nanocomposite (VAN) films have self-assembled pillar-matrix nanostructures. Owing to their large area-to-volume ratios, interfaces in VAN films are expected to play key roles in inducing functional properties, but our understanding is hindered by limited knowledge about their structures. Motivated by the lack of definitive explanation for the experimentally found enhanced ionic conductivity in Sm-doped-CeO2/SrTiO3 VAN films, we determine the structure at vertical interfaces using random structure searching and explore how it can affect ionic conduction. Interatomic potentials are used to perform the initial searching, followed by first-principles calculations for refinement. Previously unknown structures are found, with lower energy than that of an optimized hand-built model. We find a strongly distorted oxygen sublattice which gives a complex landscape of vacancy energies. The cation lattice remains similar to the bulk phase, but has a localized strain field. The excess energy of the interface is similar to that of high angle grain boundaries in SrTiO3.China Scholarship Council Cambridge Commonwealth, European and International Trus

Improving polymer solar cell performances by manipulating the self-organization of polymer

We have investigated driving force effects on the ordering of polymer, which is a key factor of self-assembly of soft materials. By turning the substrate up-side-down, the downward driving force can form in solution film-growth process and affect the self-organization of polymer chains and domains. We introduce Brown's capillarity theory [J. Polym. Sci., Polym. Phys. Ed. 22, 423 (1956)] to describe the film formation. Our results show that the better chain and lamellae packing of polymer make hole transport, carrier balance, and power conversion efficiency of annealed and unannealed devices improve even with thick active-layers as compared to conventional devices. © 2011 American Institute of Physics.published_or_final_versio

The Reform of Employee Compensation in China’s Industrial Enterprises

Although employee compensation reform in Chinese industrial sector has been discussed in the literature, the real changes in compensation system and pay practices have received insufficient attention and warrant further examination. This paper briefly reviews the pre- and post-reform compensation system, and reports the results of a survey of pay practices in the four major types of industrial enterprises in China. The research findings indicate that the type of enterprise ownership has little influence on general compensation practices, adoption of profit-sharing plans, and subsidy and allowance packages. In general, pay is linked more to individual performance and has become an important incentive to Chinese employees. However, differences are found across the enterprise types with regard to performance-related pay. Current pay practices are positively correlated to overall effectiveness of the enterprise

A Self-Reference False Memory Effect in the DRM Paradigm: Evidence from Eastern and Western Samples

It is well established that processing information in relation to oneself (i.e., selfreferencing) leads to better memory for that information than processing that same information in relation to others (i.e., other-referencing). However, it is unknown whether self-referencing also leads to more false memories than other-referencing. In the current two experiments with European and East Asian samples, we presented participants the Deese-Roediger/McDermott (DRM) lists together with their own name or other people’s name (i.e., “Trump” in Experiment 1 and “Li Ming” in Experiment 2). We found consistent results across the two experiments; that is, in the self-reference condition, participants had higher true and false memory rates compared to those in the other-reference condition. Moreover, we found that selfreferencing did not exhibit superior mnemonic advantage in terms of net accuracy compared to other-referencing and neutral conditions. These findings are discussed in terms of theoretical frameworks such as spreading activation theories and the fuzzytrace theory. We propose that our results reflect the adaptive nature of memory in the sense that cognitive processes that increase mnemonic efficiency may also increase susceptibility to associative false memories

Evaluation of growth methods for the heteroepitaxy of non-polar (1120) GAN on sapphire by MOVPE

Non-polar a-plane gallium nitride (GaN) lms have been grown on r-plane (1102) sapphire by metal organic vapour phase epitaxy (MOVPE). A total of ve in-situ defect reduction techniques for a-plane GaN are compared, including two variants with a low temperature GaN nucleation layer (LTNL) and three variants without LTNL, in which the high- temperature growth of GaN is performed directly on the sapphire using various crystallite sizes. The material quality is investigated by photoluminescence (PL), x-ray di raction, cathodoluminescence, atomic force and optical microscopy. It is found that all layers are anisotropically strained with threading dislocation densities over 109 cm2. The PL spectrum is typically dominated by emission from basal plane stacking faults. Overall, growth techniques without LTNL do not yield any particular improvement and even result in the creation of new defects, ie. inversion domains, which are seldom observed if a low temperature GaN nucleation layer is used. The best growth method uses a LTNL combined with a single silicon nitride interlayer.This work is supported by the Engineering and Physical Sciences Research Council (United Kingdom) under EP/J003603/1 and EP/H0495331. The European Research Council has also provided nancial support under the European Community's Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement no 279361 (MACONS).This is the final published version, also available from Elsevier at: http://dx.doi.org/10.1016/j.jcrysgro.2014.09.00

Growth of non-polar (11-20) InGaN quantum dots by metal organic vapour phase epitaxy using a two temperature method

Non-polar (11-20) InGaN quantum dots (QDs) were grown by metal organic vapour phase epitaxy. An InGaN epilayer was grown and subjected to a temperature ramp in a nitrogen and ammonia environment before the growth of the GaN capping layer. Uncapped structures with and without the temperature ramp were grown for reference and imaged by atomic force microscopy. Micro-photoluminescence studies reveal the presence of resolution limited peaks with a linewidth of less than ∼500 μeV at 4.2 K. This linewidth is significantly narrower than that of non-polar InGaN quantum dots grown by alternate methods and may be indicative of reduced spectral diffusion. Time resolved photoluminescence studies reveal a mono-exponential exciton decay with a lifetime of 533 ps at 2.70 eV. The excitonic lifetime is more than an order of magnitude shorter than that for previously studied polar quantum dots and suggests the suppression of the internal electric field. Cathodoluminescence studies show the spatial distribution of the quantum dots and resolution limited spectral peaks at 18 K.This work was funded by the EPSRC (Grant Nos. EP/J003603/1 and EP/H047816/1).This is the final published version. It first appeared at http://scitation.aip.org/content/aip/journal/aplmater/2/12/10.1063/1.4904068