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At least 1,207 records · Page 67

Dislocation-θ' (Al2Cu) interactions during creep deformation of an Al-Cu alloy

While precipitate-dislocation interactions are well-understood for Al-Cu alloys in tension, creep behavior has seen far less study. New, thermally-stabilized Al-Cu alloys have θ' (Al 2 Cu) as strengthening precipitates that remain stable up to 300 °C (~60% of the melting temperature) and higher, where creep becomes essential to the mechanical behavior. This investigation identifies the precipitate-dislocation interactions in such an Al-Cu alloy using in-situ neutron diffraction and scanning transmission electron microscopy. Significant load transfer to the θ' precipitates occurs, which can be attributed to dislocation loops on the interfaces of θ' and the Al matrix. Thus, Orowan looping is identified to be the primary activity for precipitate-dislocation interactions. As Orowan looping and load transfer are associated with significant strain hardening, these results explain the excellent creep resistance seen in this alloy, and provide insights into the design of precipitation strengthened alloys with superior creep performance.

36 MATERIALS SCIENCE↗

DNA origami protection and molecular interfacing through engineered sequence-defined peptoids

DNA nanotechnology has established approaches for designing programmable and precisely controlled nanoscale architectures through specific Watson−Crick base-pairing, molecular plasticity, and intermolecular connectivity. In particular, superior control over DNA origami structures could be beneficial for biomedical applications, including biosensing, in vivo imaging, and drug and gene delivery. However, protecting DNA origami structures in complex biological fluids while preserving their structural characteristics remains a major challenge for enabling these applications. Here, we developed a class of structurally well-defined peptoids to protect DNA origamis in ionic and bioactive conditions and systematically explored the effects of peptoid architecture and sequence dependency on DNA origami stability. The applicability of this approach for drug delivery, bioimaging, and cell targeting was also demonstrated. A series of peptoids (PE1–9) with two types of architectures, termed as “brush” and “block,” were built from positively charged monomers and neutral oligo-ethyleneoxy monomers, where certain designs were found to greatly enhance the stability of DNA origami. Through experimental and molecular dynamics studies, we demonstrated the role of sequence-dependent electrostatic interactions of peptoids with the DNA backbone. We showed that octahedral DNA origamis coated with peptoid (PE2) can be used as carriers for anticancer drug and protein, where the peptoid modulated the rate of drug release and prolonged protein stability against proteolytic hydrolysis. Finally, we synthesized two alkyne-modified peptoids (PE8 and PE9), conjugated with fluorophore and antibody, to make stable DNA origamis with imaging and cell-targeting capabilities. Our results demonstrate an approach toward functional and physiologically stable DNA origami for biomedical applications.

36 MATERIALS SCIENCE↗

Enabling AC electroluminescence in quasi-2D perovskites by uniformly arranging different-n-value nanoplates to allow bidirectional charge transport

Perovskite light-emitting diodes (LEDs) are normally operated under forward direct current (DC) to realize electron/hole injection at cathode/anode surfaces. In this work, we demonstrate an alternating current (AC) driven LED enabled by bi-directionally allowed charge transport in quasi-2D perovskite (PEA 2 MA n-1 PbnI 3n+1 ) film. Essentially, the bi-directional charge transport is realized by uniformly arranging different-n-value 2D nanoplates together with symmetrically designed anode/cathode interfaces, which can allow injected electrons and holes to form light-emitting states under both forward and reverse biases, leading to an AC electroluminescence (EL) with the device architecture of ITO/PEI/PEDOT:PSS/PEA 2 MA n-1 PbnI 3n+1 /P3HT/PEI/Ag. The high AC EL performance was achieved with the radiance = 24 W Sr -1 m -2 and 18.3 W Sr -1 m -2 and EQE = 12.5% and 3.7% under forward and reverse biases. Furthermore, the device-operational stability was largely improved with the half-intensity time of T 50 = 11.0 h under AC bias (+2 V/-2 V, 50 Hz) as compared to T 50 = 3.9 h under forward bias (+2 V/0 V, 50 Hz).

36 MATERIALS SCIENCE↗

Status Report on the Development of Cladding Inner-wall and Outer-wall Coatings

Advanced cladding is critical for nuclear reactors with enhanced performance in radiation tolerance, neutron transparency and reactor safety. Using advanced cladding will ensure the adequate thermal conductivity and mechanical stability of the cladding base material, corrosion resistance and high-temperature coolant compatibility of the cladding surface, and chemical stability in the cladding inner wall against fuel cladding chemical interaction (FCCI). An innovative cladding with a three-layer structure (i.e., a modified outer surface, a robust clad base material, and a modified inner wall) promises to meet all these requirements. In this status report, the initial efforts on the development of cladding inner-wall and outer-wall coatings are summarized. The activities covered in this report are (1) High-resolution TEM studies of TiN/HT-9 interface atomic structure and chemistry after ion irradiation, (2) High-resolution TEM studies of TiN/14YWT ODS interface atomic structure after thermal cycling, (3) Inner-wall TiN coating for an experimental 14YWT ODS cladding, and (4) Corrosion test of TiN coated Ziracloy-4 bar samples.

36 - MATERIALS SCIENCE↗

Optimized Al Doping Improves Both Interphase Stability and Bulk Structural Integrity of Ni-Rich NMC Cathode Materials

Ni-rich layered transition metal oxide (NMC, LiNi1-x-yMxCoyO2, 1 – x – y = 0.6) is promising for high-energy-density lithium-ion batteries, but its large-scale application is still hindered by several technical challenges, including secondary particle cracking, interfacial instability, and cell degassing during cycling. Here, we report a facile wet-chemical method to modify both the surface and the bulk of the LiNi0.76Mn0.14Co0.10O2 (NMC76) cathode with Al doping to effectively improve the structural/interfacial stability of the cathode, and hence its long-term cycling capability. With only 1 mol% Al doping, the Al-NMC76 electrode delivers a good capacity retention of 79.2% after 500 cycles at a high voltage limit of 4.5 V, which is far better than those of undoped NMC76 under the similar condition. The enhanced performance can be attributed to the Al doping in the NMC76, which not only strengthens the bulk structural stability through doping into the lattice, but also suppresses acidic attack from the electrolyte through altered surface structure of NMC76.

Al doping, capacity retention, high voltage, elect↗

Implementation of Advanced Grid Support Functionalities by Smart Operation of Residential Loads with low Cost Converter Interface

This paper investigates a grid-supportive load concept for small-scale residential appliances, focusing on a residential refrigerator. Power consumption is adjusted based on grid conditions to achieve IEEE-1547 grid support functions. Two key aspects are presented: a low-cost refrigerator converter with Lyapunov energy function-based local controllers for speed control, and the impact on a standard microgrid system, demonstrating advanced grid support from the load side. This method enhances grid resilience and reliability and can be extended to other residential loads. The study contributes to efficient and robust grid-supportive load management systems, showing promising performance. This approach has the potential to improve overall grid stability and can be adapted for various types of residential appliances. The modeling and simulations in MATLAB/Simulink and PLECS confirm the feasibility and effectiveness of the proposed solution. Future work will explore real-world implementation and scalability of this concept for broader applications.

grid supportive loads (GSL)↗

Continuum gyrokinetic simulations of edge plasmas in single-null geometries

The first continuum gyrokinetic calculations of electrostatic ion scale turbulence are presented for the case of a diverted tokamak geometry. The simulation model solves the long-wavelength limit of the full-F gyrokinetic equation for ion species coupled to the quasi-neutrality equation for electrostatic potential variations, where a fluid model is used for an electron response. Furthermore, in order to facilitate simulations of highly-anisotropic microturbulence in the presence of strong magnetic shear and a magnetic X-point, a numerical algorithm utilizing a locally field-aligned multiblock coordinate system has been developed and implemented in the 5D finite-volume code COGENT. In this approach, the toroidal direction is divided into blocks, such that within each block, the cells are field-aligned and a non-matching grid interface is allowed at block boundaries. The toroidal angle corresponds to the “coarse” field-aligned coordinate, whereas the poloidal cross section, comprised of the radial and poloidal directions, is finely gridded to resolve short-scale perpendicular turbulence structures and to support accurate re-mapping (interpolation) at block boundaries. The 5D simulations explore cross-separatrix ion scale turbulence in the presence of a self-consistent radial electric field and address the effects of magnetic-shear stabilization in the X-point region.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Convection-Induced Compositional Patterning at Grain Boundaries in Irradiated Alloys

We consider the stability of precipitates formed at grain boundaries (GBs) by radiation-induced segregation in dilute alloys subjected to irradiation. Here, the effects of grain size and misorientation of symmetric-tilt GBs are quantified using phase field modeling. A novel regime is identified where, at long times, GBs are decorated by precipitate patterns that resist coarsening. Maps of the chemical Péclet number indicate that arrested coarsening takes place when solute advection dominates over thermal diffusion right up to the precipitate/matrix interface, preventing interfacial local equilibrium and overriding capillary effects. This contrasts with liquid-solid mixtures where convection always accelerates coarsening.

36 MATERIALS SCIENCE↗

Interphase Stabilization of LiNi 0.5 Mn 1.5 O 4 Cathode for 5 V–Class All–Solid–State Batteries

Employing high voltage cobalt-free spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) as a cathode is promising for high energy density and cost-effectiveness, but it has challenges in all-solid-state batteries (ASSBs). Here, it is revealed that the limitation of lithium argyrodite sulfide solid electrolyte (Li 6 PS 5 Cl) with the LNMO cathode is due to the intrinsic chemical incompatibility and poor oxidative stability. Through a careful analysis of the interphase of LNMO, it is elucidated that even the halide solid electrolyte (Li 3 InCl 6 ) with high oxidative stability can be decomposed to form resistive interphase layers with LNMO in ASSBs. Interestingly, with Fe-doping and a Li 3 PO 4 protective layer coating, LNMO with Li 3 InCl 6 displays stable cycle performance with a stabilized interphase at a high voltage (≈4.7 V) in ASSBs. The enhanced interfacial stability with the extended electrochemical stability window through doping and coating enables high electrochemical stability with LNMO in ASSBs. Furthermore, this work provides guidance for employing high-voltage cathodes in ASSBs and highlights the importance of stable interphases to enable stable cycling in ASSBs.

25 ENERGY STORAGE↗

On the distribution of stacking faults at dissociated medium-angle grain boundaries: Crystallographic geometry and metastability

Grain boundaries in FCC metals with low stacking-fault energy can form in dissociated configurations of stacking faults. Perhaps the most studied example is 9R stacking at boundaries near Σ3{112}, where the distribution of stacking faults is related to the emission of Shockley partial dislocations. Here, we combine atomic-resolution electron microscopy, atomistic simulations, and dislocation theory to demonstrate that boundaries vicinal to Σ33a support the stabilization of dissociated 9R stacking within a narrow range of inclinations. This boundary is interesting since its misorientation (20.05°) lies in the medium-angle regime, just past the upper misorientation limit for low-angle boundaries, motivating questions for how best to describe it in terms of dislocations. Our HAADF-STEM observations of thin film bicrystals, supported by atomistic modeling, reveal that this inclination dependence arises from specific geometric constraints on the arrangement of Shockley partial dislocations at the interface. Quantification of stacking-fault distributions across multiple boundaries indicates that the density and spacing of faults closely follow the ideal 9R motif, with subtle variations reflecting the complex energy landscape of these boundaries. Through energetic analysis, we establish the presence of competing metastable states enabled by variations in stacking sequences, emphasizing the significant role of crystallographic geometry. We generalize our analysis as a function of misorientation, showing how 9R at the Σ33a boundary is related to previous observations and calculations of HCP at a 29.7° boundary. This study provides a crystallographically grounded framework connecting dislocation structures, stacking-fault distributions, and metastability at grain boundaries in FCC metals.

Atomistic modeling↗

Investigation of the Self-Assembly Behavior of Statistical Bottlebrush Copolymers via Self-Consistent Field Theory Simulations

Bottlebrush copolymers, a class of high-density side-chain-grafted copolymers with high molecular weights, have recently attracted extensive research attention due to the dramatic reduction of chain entanglement in these copolymers, unique self-assembly behaviors, and distinctive physical properties. In this study, we employ self-consistent field theory simulations to systemically investigate the phase behavior of statistical bottlebrush copolymers A-stat-B, an intriguing subclass of bottlebrush copolymers with random or alternating sequences of A and B side chains. We find that a broader variety of ordered mesophases can be stabilized in the melts of these copolymers relative to the more extensively studied bottlebrush block copolymers. In particular, we observe that these statistical copolymers can stabilize sphere phases over a larger range of species volume fractions than their diblock and tetrablock counterparts but require much higher segregation strength to achieve this. The sphere and hexagonally packed cylinder phases formed by conformationally symmetric statistical bottlebrush copolymers possess interesting discrete core–shell structures with the backbone and lower volume fraction side-chain species forming shells and cores, respectively. Moreover, we uncover a new strategy of stabilizing the Frank–Kasper phase A15 by introducing conformational asymmetry through different side-chain lengths and also observe deflection of order–order phase boundaries and significant mixing between the backbones and short side chains as conformational asymmetry is introduced.

36 MATERIALS SCIENCE↗

Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates

Utilizing the self-assembly of block copolymers with large Flory–Huggins interaction parameters (χ) for nanofabrication is a formidable challenge due to the attendant large surface energy differences between the blocks. This work reports a robust protocol for the fabrication of thin films with highly ordered cylindrical nanopore arrays via the self-assembly of an asymmetric poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) diblock copolymer blended with a P4VP homopolymer. The desired vertical domain orientation is achieved at the air–polymer interface by controlled solvent vapor annealing (SVA) using acetone, a solvent with weak selectivity for PS over P4VP, and at the substrate interface by functionalization using a hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) homopolymer brush. In contrast, the vertical cylinder orientation is unstable during acetone SVA on substrates functionalized using hydroxy-terminated poly(methyl methacrylate) (PMMA-OH). Although PMMA exhibits more balanced interfacial energies between PS and P4VP than P2VP in the dry state, it is also swollen more selectively by acetone. We hypothesize that the nearly balanced solvent swelling of the three polymers (P2VP, P4VP, and PS) stabilizes the vertical cylinder orientation, while unbalanced swelling (PMMA > P4VP and PS) does not. Here we further characterize pore formation by addition of a P4VP homopolymer and its postassembly extraction using ethanol, revealing a narrow window of pore size tunability. Notably, minimal differences in nanopore morphologies are observed for P4VP volume fractions as high as 0.1, regardless of the P4VP molar mass. However, further increasing the P4VP volume fraction results in domain reorientation or macrophase separation when its molar mass is less than or greater than the P4VP block molar mass, respectively. Using a P4VP homopolymer that is nearly equal in length to the P4VP block enables the fabrication of well-ordered arrays of vertical, through-film nanopores with high aspect ratios (>10), small periods (<23 nm), and diameters less than 10 nm.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The coupling and competition of crystallization and phase separation, correlating thermodynamics and kinetics in OPV morphology and performances

The active layer morphology transition of organic photovoltaics under non-equilibrium conditions are of vital importance in determining the device power conversion efficiency and stability; however, a general and unified picture on this issue has not been well addressed. Using combined in situ and ex situ morphology characterizations, morphological parameters relating to kinetics and thermodynamics of morphology evolution are extracted and studied in model systems under thermal annealing. The coupling and competition of crystallization and demixing are found to be critical in morphology evolution, phase purification and interfacial orientation. A unified model summarizing different phase diagrams and all possible kinetic routes is proposed. The current observations address the fundamental issues underlying the formation of the complex multi-length scale morphology in bulk heterojunction blends and provide useful morphology optimization guidelines for processing devices with higher efficiency and stability.

36 MATERIALS SCIENCE↗

Hydropower Geotechnical Foundations: Current Practice and Innovation Opportunities for Low-Head Applications

Hydropower is a renewable energy resource that produces electricity from flowing water under pressure. Engineered hydropower structures, such as dams, are used to create a hydraulic head, enabling a turbinegenerator unit to convert pressurized flow into electricity. While hydropower has been a source of renewable energy since antiquity, new development in the United States has slowed in recent decades. Based on recent resource assessments, the largest opportunity to expand hydropower in the United States is from new stream-reach development (i.e., new hydropower development along stream-reaches that do not currently have hydroelectric facilities or other forms of infrastructure, such as dams). Roughly 75% of identified new stream-reach development potential is from low-head sites (less than 30 ft of head), which typically suffer from smaller power densities and higher normalized costs, given economies of scale. Hydropower developers and other stakeholders are thus interested in strategies to reduce initial capital costs while practicing sustainable development to maximize environmental compatibility with minimal disruption to natural aquatic life, sediment, and water flows. Historically, civil works have represented a significant cost driver for new hydropower development, with the foundation system representing a major cost component and source of uncertainty. The foundation system is the collection of engineered structural features (e.g. cutoff trenches, walls, grouting, anchors) constructed at or below the preconstruction ground surface that interfaces between the overlying structures (superstructures) and the bed material below (subsurface). Development of a hydropower foundation system must consider the various characteristics of the surrounding stream environment and subsurface while adhering to the engineering requirements of the superstructure that it supports. The care of water, excavation, and other construction activities are important features of foundation design and construction. The design and construction cost of the foundation system is largely dependent on the site geology and riverbed composition and is influenced by the level of geotechnical assessment required and conducted. Thus, a hydropower facility’s geotechnical foundation is often highly site-specific, with proper site selection and assessment being important to project success. The foundation system is designed to provide structural stability (of the foundation and dam), limit seepage, ensure public safety, and maintain functionality for the project life, during both construction and facility operations. Inadequate foundation or dam design can result in dam failure and the uncontrolled release of significant volumes of water, which could cause a high number of casualties and extensive property damage downstream of the failure. According to the Association of State Dam Safety Officials, approximately 30% of all historical dam failures in the United States are attributed to foundation or abutment defects, and another 20% are attributed to piping or seepage through the embankment, foundation, or abutment. To ameliorate these safety considerations, foundations often require massive amounts of construction material (e.g., grout, concrete, engineered dam fill) and long construction times. Foundation design also requires significant analysis prior to construction because the initial in-stream and abutment subsurface conditions are site-specific, and sufficient data for them often are lacking. Current practice requires on-site assessment, using expensive drilling and invasive and non-invasive investigation methods, to determine the expected cost of foundation material and treatment. Additionally, foundation construction often requires site dewatering (and other care of water activities), which involves constructing temporary diversion structures upstream and often downstream, called cofferdams, and water diversion systems that route water around the construction site. Cofferdams and water diversion systems can drastically increase construction costs and contribute to environmental disruption, including modification of flow patterns and benthic habitats. Given the technical, economic, and environmental challenges associated with hydropower foundations, opportunities exist to improve the current state of practice and to develop new and innovative solutions to Hydropower is a renewable energy resource that produces electricity from flowing water under pressure. Engineered hydropower structures, such as dams, are used to create a hydraulic head, enabling a turbinegenerator unit to convert pressurized flow into electricity. While hydropower has been a source of renewable energy since antiquity, new development in the United States has slowed in recent decades. Based on recent resource assessments, the largest opportunity to expand hydropower in the United States is from new stream-reach development (i.e., new hydropower development along stream-reaches that do not currently have hydroelectric facilities or other forms of infrastructure, such as dams). Roughly 75% of identified new stream-reach development potential is from low-head sites (less than 30 ft of head), which typically suffer from smaller power densities and higher normalized costs, given economies of scale. Hydropower developers and other stakeholders are thus interested in strategies to reduce initial capital costs while practicing sustainable development to maximize environmental compatibility with minimal disruption to natural aquatic life, sediment, and water flows. Historically, civil works have represented a significant cost driver for new hydropower development, with the foundation system representing a major cost component and source of uncertainty. The foundation system is the collection of engineered structural features (e.g. cutoff trenches, walls, grouting, anchors) constructed at or below the preconstruction ground surface that interfaces between the overlying structures (superstructures) and the bed material below (subsurface). Development of a hydropower foundation system must consider the various characteristics of the surrounding stream environment and subsurface while adhering to the engineering requirements of the superstructure that it supports. The care of water, excavation, and other construction activities are important features of foundation design and construction. The design and construction cost of the foundation system is largely dependent on the site geology and riverbed composition and is influenced by the level of geotechnical assessment required and conducted. Thus, a hydropower facility’s geotechnical foundation is often highly site-specific, with proper site selection and assessment being important to project success. The foundation system is designed to provide structural stability (of the foundation and dam), limit seepage, ensure public safety, and maintain functionality for the project life, during both construction and facility operations. Inadequate foundation or dam design can result in dam failure and the uncontrolled release of significant volumes of water, which could cause a high number of casualties and extensive property damage downstream of the failure. According to the Association of State Dam Safety Officials, approximately 30% of all historical dam failures in the United States are attributed to foundation or abutment defects, and another 20% are attributed to piping or seepage through the embankment, foundation, or abutment. To ameliorate these safety considerations, foundations often require massive amounts of construction material (e.g., grout, concrete, engineered dam fill) and long construction times. Foundation design also requires significant analysis prior to construction because the initial in-stream and abutment subsurface conditions are site-specific, and sufficient data for them often are lacking. Current practice requires on-site assessment, using expensive drilling and invasive and non-invasive investigation methods, to determine the expected cost of foundation material and treatment. Additionally, foundation construction often requires site dewatering (and other care of water activities), which involves constructing temporary diversion structures upstream and often downstream, called cofferdams, and water diversion systems that route water around the construction site. Cofferdams and water diversion systems can drastically increase construction costs and contribute to environmental disruption, including modification of flow patterns and benthic habitats. Given the technical, economic, and environmental challenges associated with hydropower foundations, opportunities exist to improve the current state of practice and to develop new and innovative solutions to challenges frequently encountered with traditional approaches. With this understanding, it is critically important to understand and document the current state of practice for hydropower geotechnical foundations, identify key challenges, and define opportunities for innovative solutions. To this end, this report documents the current state of practice across the three main phases of geotechnical foundation development: (1) geotechnical site assessment, (2) design, and (3) construction for hydropower systems. It also describes the major challenges with conventional approaches and identifies opportunities for innovation to reduce hydropower foundations costs, timelines, and risks. Key takeaways from this report include the following: Approximately 80% of available low-head sites are expected to have foundations on soil beds rather than rock beds, suggesting that rockfill and earthfill dams may be the most cost-effective conventional dam type for new projects.; Geotechnical and geologic investigation activities are time-consuming and expensive but are essential to define the parameters and criteria needed for foundation design.; Certain riverbed soil and bedrock types present significant technical challenges or require expensive foundation construction, which can prove financially prohibitive for low-head project development.; Modular hydropower design and prefabricated modular foundations represent a promising but unproven paradigm for new hydropower development. Design and construction approaches using optimized and highly repeatable, reliable components would benefit project cost, time, and risk but require additional research and development.; Temporary construction features for foundations, including cofferdams, water diversion, and water control systems, can prove costly and have inherent construction risk.; For economically viable development, hydropower geotechnical foundations should be limited to 4 to 15% of the project’s total initial capital costs. Many proposed projects have experienced cost overruns attributable to foundation difficulties or surprises during construction. These overruns may have been due to inadequate investigations, lack of adequate engineering effort to tailor the structures to site geology and topography, and/or contractual terms, among other considerations.; Challenges for hydropower foundations and opportunities for innovative technology solutions are identified in the following areas (consistent with the three main phases of foundation development): Geotechnical site assessment, Foundation design and materials, Construction methods and technology. Ultimately, this report aims to provide information about geotechnical foundations for low-head hydropower and to motivate transformative technologies to support hydropower growth.

13 HYDRO ENERGY↗

Conformationally Adaptable Extractant Flexes Strong Lanthanide Reverse-Size Selectivity

Chemical selectivity is traditionally understood in the context of rigid molecular scaffolds with precisely defined local coordination and chemical environments that ultimately facilitate a given transformation of interest. By contrast, nature leverages dynamic structures and strong coupling to enable specific interactions with target species in otherwise complex media. Taking inspiration from nature, we demonstrate unconventional selectivity in the solvent extraction of light over heavy lanthanides using a conformationally flexible ligand called octadecyl acyclopa (ODA). This novel ligand forms pseudocyclic molecular complexes with lanthanide ions at organic/aqueous interfaces, revealed by vibrational sum frequency generation spectroscopy. These complexes are extracted into the organic phase, where femtosecond structural dynamics are probed by two-dimensional infrared spectroscopy and ab initio molecular dynamics simulations to mechanistically frame the macroscopic selectivity trends. We find larger-than-expected structural fluctuations and bond lengths for heavy Ln–ODA complexes that arise from an inability of ODA to contort around the smaller ions to satisfy all would-be bonding interactions, despite forming some individually strong bonds. This finding contrasts with the binding of ODA with lighter lanthanides where, despite individually weaker bonds, collective interactions manifest that minimize structural fluctuations and give rise to enhanced thermodynamic stability. Furthermore, these results point to a new paradigm where conformational dynamics and cumulative bonding interactions can be used to facilitate unconventional chemical transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rational Design of A Chemical Bath Deposition Based Tin Oxide Electron Transport Layer for Perovskite Photovoltaics

Chemical bath deposition is widely used to deposit SnO x as an electron transport layer in perovskite solar cells (PSCs). The conventional recipe uses thioglycolic acid (TGA) to facilitate attachments of SnO x particles onto the substrate. However, nonvolatile TGA has been reported to harm the operational stability of PSCs. In this work, we introduced a volatile oxalic acid (OA) as an alternative to TGA. OA, a dicarboxylic acid, functions as a chemical linker for the nucleation and attachment of particles to the substrate in the chemical bath. Moreover, OA can be readily removed through thermal annealing followed by a mild H 2 O 2 treatment, as shown by FTIR measurements. Synergistically, the mild H 2 O 2 treatment selectively oxidizes the surface of the SnOx layer, minimizing nonradiative interface carrier recombination. EELS (electron-energy-loss-spectroscopy) confirms that the SnO x surface is dominated by Sn 4+ , while the bulk is a mixture of Sn 2+ and Sn 4+ . This rational design of a CBD SnO x layer leads to devices with T85~1,500h, a significant improvement over the TGA-based device with T80~250h. Our champion device reached a power conversion efficiency of 24.6%. This work offers a rationale for optimizing the complex parameter space of CBD SnO x to achieve efficient and stable PSCs.

14 SOLAR ENERGY↗

NASICON Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 Solid Electrolyte for an All‐Solid‐State Li‐Metal Battery

Abstract A thin solid electrolyte with a high Li + conductivity is used to separate the metallic lithium anode and the cathode in an all‐solid‐state Li‐metal battery. However, most solid Li‐ion electrolytes have a small electrochemical stability window, large interfacial resistance, and cannot block lithium‐dendrite growth when lithium is plated on charging of the cell. Mg 2+ stabilizes a rhombohedral NASICON‐structured solid electrolyte of the formula Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 (LMZP). This solid electrolyte has Li‐ion conductivity two orders of magnitude higher at 25 °C than that of the triclinic LiZr 2 (PO 4 ) 3 . 7 Li and 6 Li NMR confirm the Li‐ions in two different crystallographic sites of the NASICON framework with 85% of the Li‐ions having a relatively higher mobility than the other 15%. The anode–electrolyte interface is further investigated with symmetric Li/LMZP/Li cell testing, while the cathode–electrolyte interface is explored with an all‐solid‐state Li/LMZP/LiFePO 4 cell. The enhanced performance of these cells enabled by the Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 solid electrolyte is stable upon repeated charge/discharge cycling.

Zhou, Qiongyu↗