Atomistic Conversion Reaction Mechanism of WO3 in Secondary Ion Batteries of Li, Na, and Ca

Intercalation and conversion are two fundamental chemical processes for battery materials in response to ion insertion. The interplay between these two chemical processes has never been directly seen and understood at atomic scale. Here, using in situ HRTEM, we captured the atomistic conversion reaction processes during Li, Na, Ca insertion into a WO3 single crystal model electrode. An intercalation step prior to conversion is explicitly revealed at atomic scale for the first time for Li, Na, Ca. Nanoscale diffraction and ab initio molecular dynamic simulations revealed that after intercalation, the inserted ion–oxygen bond formation destabilizes the transition‐metal framework which gradually shrinks, distorts and finally collapses to an amorphous W and MxO (M=Li, Na, Ca) composite structure. This study provides a full atomistic picture of the transition from intercalation to conversion, which is of essential importance for both secondary ion batteries and electrochromic devices.Das Wechselspiel zwischen Ioneninterkalation und Umwandlung des WO3‐Elektrodenmaterials wurde durch In‐situ‐TEM auf atomarer Ebene untersucht. Die Bildung von Ion‐Sauerstoff‐Bindungen destabilisiert das WO3‐Gerüst: Es schrumpft, wird verzerrt und fällt schließlich zu einer amorphen W‐ und MxO‐Verbundstruktur (M=Li, Na, Ca) zusammen.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/134843/1/ange201601542_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/134843/2/ange201601542.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/134843/3/ange201601542-sup-0001-misc_information.pd

Atomistic Conversion Reaction Mechanism of WO3 in Secondary Ion Batteries of Li, Na, and Ca

Intercalation and conversion are two fundamental chemical processes for battery materials in response to ion insertion. The interplay between these two chemical processes has never been directly seen and understood at atomic scale. Here, using in situ HRTEM, we captured the atomistic conversion reaction processes during Li, Na, Ca insertion into a WO3 single crystal model electrode. An intercalation step prior to conversion is explicitly revealed at atomic scale for the first time for Li, Na, Ca. Nanoscale diffraction and ab initio molecular dynamic simulations revealed that after intercalation, the inserted ion–oxygen bond formation destabilizes the transition‐metal framework which gradually shrinks, distorts and finally collapses to an amorphous W and MxO (M=Li, Na, Ca) composite structure. This study provides a full atomistic picture of the transition from intercalation to conversion, which is of essential importance for both secondary ion batteries and electrochromic devices.The interplay between ion intercalation and WO3 battery electrode conversion was investigated at atomic scale by using in situ HRTEM. The ion–oxygen bond formation destabilizes the WO3 framework which gradually shrinks, distorts and finally collapses to an amorphous W and MxO (M=Li, Na, Ca) composite structure.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/135051/1/anie201601542.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/135051/2/anie201601542-sup-0001-misc_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/135051/3/anie201601542_am.pd

Electroplating lithium transition metal oxides.

Materials synthesis often provides opportunities for innovation. We demonstrate a general low-temperature (260°C) molten salt electrodeposition approach to directly electroplate the important lithium-ion (Li-ion) battery cathode materials LiCoO2, LiMn2O4, and Al-doped LiCoO2. The crystallinities and electrochemical capacities of the electroplated oxides are comparable to those of the powders synthesized at much higher temperatures (700° to 1000°C). This new growth method significantly broadens the scope of battery form factors and functionalities, enabling a variety of highly desirable battery properties, including high energy, high power, and unprecedented electrode flexibility

The enormous repetitive Antarctic krill genome reveals environmental adaptations and population insights

Antarctic krill (Euphausia superba) is Earth’smost abundant wild animal, and its enormous biomass is vital to the Southern Ocean ecosystem. Here, we report a 48.01-Gb chromosome-level Antarctic krill genome, whose large genome size appears to have resulted from inter-genic transposable element expansions. Our assembly reveals the molecular architecture of the Antarctic krill circadian clock and uncovers expanded gene families associated with molting and energy metabolism, providing insights into adaptations to the cold and highly seasonal Antarctic environment. Population-level genome re-sequencing from four geographical sites around the Antarctic continent reveals no clear population structure but highlights natural selection associated with environmental variables. An apparent drastic reduction in krill population size 10 mya and a subsequent rebound 100 thousand years ago coincides with climate change events. Our findings uncover the genomic basis of Antarctic krill adaptations to the Southern Ocean and provide valuable resources for future Antarctic research

Bio-inspired geotechnical engineering: Principles, current work, opportunities and challenges

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Bio-inspired geotechnical engineering: principles, current work, opportunities and challenges

A broad diversity of biological organisms and systems interact with soil in ways that facilitate their growth and survival. These interactions are made possible by strategies that enable organisms to accomplish functions that can be analogous to those required in geotechnical engineering systems. Examples include anchorage in soft and weak ground, penetration into hard and stiff subsurface materials and movement in loose sand. Since the biological strategies have been ‘vetted’ by the process of natural selection, and the functions they accomplish are governed by the same physical laws in both the natural and engineered environments, they represent a unique source of principles and design ideas for addressing geotechnical challenges. Prior to implementation as engineering solutions, however, the differences in spatial and temporal scales and material properties between the biological environment and engineered system must be addressed. Current bio-inspired geotechnics research is addressing topics such as soil excavation and penetration, soil–structure interface shearing, load transfer between foundation and anchorage elements and soils, and mass and thermal transport, having gained inspiration from organisms such as worms, clams, ants, termites, fish, snakes and plant roots. This work highlights the potential benefits to both geotechnical engineering through new or improved solutions and biology through understanding of mechanisms as a result of cross-disciplinary interactions and collaborations

Millimeter-Wave Propagation Measurement and Modeling in Indoor Corridor and Stairwell at 26 and 38 GHz

Accurate propagation characteristics are essential for future indoor millimeter-wave (mmWave) small cell network planning. This paper presents propagation measurements at 26 GHz and 38 GHz which are important candidate bands for fifth generation mmWave communication. Measurements are conducted in an indoor corridor, as well as a stairwell whose mmWave channel is seldom investigated before. In these measurements, an omnidirectional biconical antenna is used as transmitter and a steerable directional horn antenna is used as receiver. The directional and omnidirectional path loss exponents, shadow factors, cross-polarization discrimination ratios and root-mean-square delay spreads are analyzed for both line-of-sight and non-line-of-sight scenarios in both co-polarization and cross-polarization, and these characteristics are compared for different frequencies and environments. It is found obvious depolarization phenomenon in non-line-of-sight scenario for higher frequency. Compared to the corridor, the stairwell has larger path loss exponents and root-mean-square delay spreads, and the depolarization is also more evident in stairwell. The results in this paper are beneficial to building efficient and robust indoor mmWave communication systems

Revealing the Dynamics of Platinum Nanoparticle Catalysts on Carbon in Oxygen and Water Using Environmental TEM

Deactivation of supported metal nanoparticle catalysts, especially under relevant gas conditions, is a critical challenge for many technological applications, including heterogeneous catalysis, electrocatalysis, and fuel cells. It has been commonly realized that deactivation of catalysts stems from surface area loss due to particle coarsening; however, the mechanism for this remains largely unclear. Herein, we use aberration-corrected environmental transmission electron microscopy, at an atomic level, to observe in situ the dynamics of Pt catalysts under fuel cell relevant gas and temperature conditions. Particle migration and coalescence is observed to be the dominant coarsening process. In comparison with the case of H₂O, O₂ promotes Pt nanoparticle migration on the carbon surface. Surprisingly, coating Pt/carbon with a nanofilm of electrolyte (Nafion ionomer) leads to a faster migration of Pt in H₂O than in O₂, a consequence of a Nafion–carbon interface water “lubrication” effect. Atomically, the particle coalescence features reorientation of particles toward lattice matching, a process driven by orientation-dependent van der Waals forces. These results provide direct observations of the dynamics of metal nanoparticles at the critical surface/interface under relevant conditions and yield significant insights into the multiphase interaction in related technological processes