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At least 19 records

In Situ Construction of Uniform and Robust Cathode–Electrolyte Interphase for Li-Rich Layered Oxides

The high-energy-density Li-rich layered oxides (LLOs) as promising cathodes for Li-ion batteries suffer from the dissolution of transition metals (especially manganese) and severe side reactions in conventional electrolytes, which greatly deteriorate their electrochemical performance. Herein, an in situ “anchoring + pouring” synergistic cathode-electrolyte interphase (CEI) construction is realized by using 1,3,6-hexanetricarbonitrile (HTCN) and tris(trimethylsilyl) phosphate (TMSP) electrolyte additives to alleviate the challenges of an LLO (Li 1.13 Mn 0.517 Ni 0.256 Co 0.097 O 2 ). HTCN with three nitrile groups can tightly anchor transition metals by coordinative interaction to form the CEI framework, and TMSP will electrochemically decompose to reshape the CEI layer. The uniform and robust in situ constructed CEI layer can suppress the transition metal dissolution, shield the cathode against diverse side reactions, and significantly improve the overall electrochemical performance of the cathode with a discharge voltage decay of only 0.5 mV/cycle -1 . Further investigations based on a series of experimental techniques and theoretical calculations have revealed the composition of in situ constructed CEI layers and their distribution, including the enhanced HTCN anchoring effect after lattice densification of LLOs. Finally, this study provides insights into the in situ CEI construction for enhancing the performance of high-energy and high-voltage cathode materials through effective, convenient and economical electrolyte approaches.

25 ENERGY STORAGE↗

In-situ construction of ceria-metal/titanate heterostructure with controllable architectures for efficient fuel electrochemical conversion

Construction of ceria-metal/titanate heterostructure via exsolution is a promising strategy to improve the catalytic activity of titanate perovskites and broaden their applications in various energy conversion scenarios. However, the species exsolved after reduction are limited to reducible metal cations, such as Ni, Co, Fe, and precious metals. Herein, we report a modified exsolution approach for co-exsolving active oxides and metal nanoparticles from a titanate perovskite, La 0.8 Ce 0.1 Ni 0.4 Ti 0.6 O 3-δ (LCeNT). We highlight strained facet-specific CeO 2 cubes can be grown on the support after an air-annealing process with their morphology tunable by varying annealing temperature, whilst exsolution of Ni nanoparticles form subsequently following chemical/electrical reduction. An electrolyte-supported SOFC utilizing CeO 2 -Ni@LCeNT anode achieves maximum power density of 642 mW cm -2 at 900 °C in H 2 (~3% H 2 O). Exceptional robustness of the heterostructure is illustrated after running the cell in CH 4 (~3% H 2 O) for 20 h. Here this work demonstrates an intriguing pathway to constructing stable and active ceria-metal/titanate heterostructure for energy applications.

36 MATERIALS SCIENCE↗

In situ construction of conjugated polymer P3HT coupled hierarchical ZnO composite with Z-scheme enhanced visible-light photocatalytic activity

Highlights: • P3HT@H-ZnO photocatalysts were fabricated via a two-step solution method. • The P3HT@H-ZnO composite. exhibited high photodegredation of RhB under visible-light. • Enhanced photocatalytic activity attributed to the closely contacted interface between P3HT and H-ZnO and the matched band gap structure. • The fabricated P3HT@H-ZnO composite follow a Z-scheme mechanism rather than type II heterojunction. - Abstract: Conjugated polymer P3HT coupled with hierarchical ZnO (H-ZnO) photocatalysts were fabricated by a two-step solution method with assembling P3HT nanoparticles on the surface of H-ZnO micro-flowers. Optical properties revealed that the fabricated H-ZnO micro-flowers were rich in defects. The as-prepared P3HT@H-ZnO composite exhibited higher photocatalytic activity than H-ZnO for photocatalytic degradation of Rhodamine B (RhB) under visible light irradiation. The enhanced photocatalytic activity was attributed to the strengthened visible light absorption and the closely contacted interface between P3HT and H-ZnO. Based on the reactive species trapping experiments and band gap structure analysis, it can be identified that the effective separation and transfer of the photo-induced electron-hole pairs within the P3HT@H-ZnO composite follow a Z-scheme mechanism rather than type II heterojunction. The present work will provide a new insight to design Z-scheme photocatalysts with enhanced photocatalytic performance via metal-free polymers modification.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Implementation Concept of Operation for a Multi-Purpose Cassegrain Solar Concentrator, Micro-Spectrometers, and Electrostatic Neutralizers to Enable In Situ Construction Activities plus Lunar, Planetary, and Deep Space Science Exploration on the Moon

The ability to utilize regolith would support human missions to the Moon and Mars by both stabilizing the surface as well as the use of indigenous resources. Precision landing requirements include surface stabilization to prevent damage or contamination due to regolith projectiles as a result of plume interaction with regolith. The use of indigenous resources rather than hauling materials from Earth appears to be economically a palatable option by converting indigenous resources to usable products. However, such activities have new technical challenges to overcome the issues related to lunar environmental conditions, a wide range of temperature fluctuation, extremely high vacuum, and electrostatically charged fine regolith dusts. For both the regolith sintering and extraction of resources onsite, a Cassegrain solar concentrator was studied for not only sintering lunar regolith into a hardened stabilized surface, but also other multiple applications. This report illustrates a Cassegrain solar concentrator that has multi-functional capabilities for space missions. Proper design and implementation of high-performance lightweight composite materials for the primary mirror of the Cassegrain concentrator can offer multiple capabilities to be performed on the Moon. The multiple applications studied with Cassegrain concentrators are (1) Solar sintering for landing pad and habitats, (2) Harvest of volatiles: H2O, O2, H2, and He-3, (3) Space antenna for telemetry and telecommunication, and (4) Space telescope with 20-meter aperture that exceeds the space telescopes to date in terms of the State-of-Art (SOA) in resolution and aperture diameter. In this study, a key emphasis was placed on the NASA Langley-developed boron nitride nanotube (BNNT) nanocomposite technology which is ideal for the segmented primary mirror structure of the Cassegrain system because it promises a very low coefficient of thermal expansion (CTE) and negligible Poisson ratio. Also, BNNT nanocomposites offer several noticeable benefits, such as light weight, radiation shielding capability, and mechanical strength for structural applications. Additionally, the NASA Langley-developed bullet-like micro-spectrometer and electrostatic power generator were reviewed for mineral mapping applications and electrostatic power generation and dust mitigation from electrostatically charged regolith.

landing pad↗

In-Situ Surface Construction of Infrastructure

In situ resources offer an opportunity to reduce the amount of items brought from Earth when exploring moons and planets. Utilizing those resources requires energy that comes with a cost. In the case of human missions to Mars, trading surface power for launch mass is beneficial for propellant and consumables required to sustain human pioneering and settlement on the planet’s surface. However, In Situ Resource Utilization (ISRU) can mean far more than propellant production and consumables replacement for missions beyond Low Earth Orbit. NASA’s Systems Capability Leader-ship Team (SCLT) for ISRU created a work break-down structure based on functions identified in roadmaps pertaining to human exploration. That WBS includes Prospecting, Extraction, Processing, Construction, Manufacturing, and Energy. Over the years, NASA has developed some capabilities and technologies for prospecting, extraction, and processing carbon dioxide and water on Mars into propellants and life support consumables. However, that is a small subset of the ISRU needs that are coming to light with NASA’s push to return to the Moon for extended periods of time. For instance, astronauts require shielding from Ga-lactic Cosmic Rays and nuclear radiation and protection from the low temperatures and pressures in Space. Surface assets including crew, landers, and ascent modules can be damaged by surface ejecta during landing and launch operations on the Moon and Mars. Creating shielding, berms, and pads requires movement of large volumes and stabilization of regolith in the context of a civil engineering construction project. Because of the multi-disciplinary nature of the aerospace systems needed for human exploration, SCLT on ISRU created an ISRU Construction Integrated Steering Group that combines expertise among several NASA Principal Technologists and Capabilities Leaders for exploring options, assessing opportunities, and developing requirements for construction and manufacturing on the Moon and Mars NASA’s new program to develop Lunar landers for small, mid, and large payload deliveries to the Lunar surface leading to human missions by 2025 spawned an investigation into plume surface interactions caused by the lander during descent and ascent. The trade space to resolve this issue includes regolith stabilization via landing pad construction techniques and lander nozzles characteristics due to vehicle systems design. Some data exists from the Apollo missions but more is required for the missions ahead. The purpose of this paper [1] is to outline an approach for developing requirements that can guide systems designs while taking advantage of flight opportunities in NASA’s plans to return to the Moon.

In-Situ↗

Playing with DIRT: Building the Framework for a Comprehensive In-Situ Soil Materials Testing Database

Long-term, sustainable planetary exploration will require the ability to "live off the land," relying on In-Situ Resource Utilization (ISRU) and In-Situ Construction as core capabilities. Reduction of both risk and launch mass for lunar construction will require evaluating and comparing regolith materials for use as feedstocks suitable for in-situ beneficiation and fabrication of building components. These material assessment capabilities will inform lunar infrastructure design decisions, with co-benefits for terrestrial construction using in-situ materials. Current planetary construction technology development relies on lunar mapping and orbital data, Apollo-era sample analyses, current simulant inventories, and tests conducted using analog site soils. Requirements for lunar infrastructure design decisions and construction systems will be determined based on specific environmental conditions, mission architectures, and the materials available within traverse range of lunar feedstock processing depots. Critical for success is the capability to identify, evaluate and make effective use of a wide range of materials as they are found in-situ on the lunar surface. This paper discusses the development of a digital repository for data on soil and regolith properties, beginning with their structural performance in both cementitious and non-cementitious building material formulations. The Database for In-situ Resource Testing (DIRT) compiles a catalog of raw materials, additives, and formulations, with notations pertaining to material sources and preparation techniques entered via a web-based user interface. Design of consistent data schemas for site-sourced materials evaluation will facilitate linkage with relevant terrestrial and planetary materials databases while enabling guided data input via templates for participation by broader groups of collaborators. Results of these analyses are compiled in a centralized repository to generate insights applicable for regolith resources and landing sites yet to be precisely defined. Collection of thorough records of material characteristics, applications and performance will support innovative construction solutions not only for space infrastructure but for sustainable, resilient design in the terrestrial built environment.

Sarah Joey Seitz↗

3D Additive Construction with Regolith for Surface Systems

Planetary surface exploration on Asteroids, the Moon, Mars and Martian Moons will require the stabilization of loose, fine, dusty regolith to avoid the effects of vertical lander rocket plume impingement, to keep abrasive and harmful dust from getting lofted and for dust free operations. In addition, the same regolith stabilization process can be used for 3 Dimensional ( 3D) printing, additive construction techniques by repeating the 2D stabilization in many vertical layers. This will allow in-situ construction with regolith so that materials will not have to be transported from Earth. Recent work in the NASA Kennedy Space Center (KSC) Surface Systems Office (NE-S) Swamp Works and at the University of Southern California (USC) under two NASA Innovative Advanced Concept (NIAC) awards have shown promising results with regolith (crushed basalt rock) materials for in-situ heat shields, bricks, landing/launch pads, berms, roads, and other structures that could be fabricated using regolith that is sintered or mixed with a polymer binder. The technical goals and objectives of this project are to prove the feasibility of 3D printing additive construction using planetary regolith simulants and to show that they have structural integrity and practical applications in space exploration.

Technology Portfolio System↗

Lattice Oxygen Redox Reversibility Modulation in Enhancing the Cycling Stability of Li-Rich Cathode Materials

The practical application of lithium-rich layered oxides is prohibited by the drawbacks such as severe capacity and voltage degradation resulting from unstable oxygen redox environment and the accompanied irreversible oxygen release. In this report a facile and effective strategy is proposed to regulate the oxygen redox chemistry via foreign Fe doping and its induced intrinsic transition metal (TM) doping as well as the in situ constructed spinel surface layer. The Fe doping, together with the induced intrinsic TM dual doping, can stabilize the lattice oxygen in the bulk due to the formed stronger Fe—O bond, and restrain the irreversible TM migration and then the undesirable phase transformation. More importantly, thermodynamical energy barrier of oxygen activation is dramatically decreased by the O 2p–Fe 3d charge-transfer, allowing stable oxygen redox activity. And the pre-constructed spinel layer can effectively stabilize the surface lattice oxygen and suppress harmful interfacial side-reactions. Such a simple optimizing method make the modified cathode exhibit a high specific capacity of 298 mAh g -1 at 0.2 C, outstanding cycling stability with a superior capacity and voltage retentions of 92.5% and 90.8%, respectively, after 400 cycles at 1 C. This study provides a new direction for developing advanced Li-ion batteries.

25 ENERGY STORAGE↗

A Universal Design of Lithium Anode via Dynamic Stability Strategy for Practical All‐Solid‐State Batteries

Abstract All‐solid‐state Li‐metal battery (ASSLB) chemistry with thin solid‐state electrolyte (SSE) membranes features high energy density and intrinsic safety but suffers from severe dendrite formation and poor interface contact during cycling, which hampers the practical application of rechargeable ASSLB. Here, we propose a universal design of thin Li‐metal anode (LMA) via a dynamic stability strategy to address these issues. The ultra‐thin LMA (20 μm) is in situ constructed with uniform highly Li‐ion conductive solid‐electrolyte interphase and composite‐polymer interphase (CPI) via electroplating process. As a result, the passivation layer with poor Li‐ion conduction on Li anode can be dissolved and small surface resistance can be achieved due to the good compatibility of CPI to SSEs. The cycling of Li symmetric cell with Li 6 PS 5 Cl thin film electrolyte (<100 μm) shows a high critical current density of >2.0 mA cm −2 with excellent cycling stability at 1.0 mA cm −2 . The ASSLBs paring with Ni‐rich LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode demonstrated the feasibility of engineered LMA design by presenting good rate capability from 0.1 C to 1.0 C at room temperature, as well as long‐term cycling stability (81 % retention after 100 cycles). This work represents a general pathway to make thin dendrite‐free LMA available for high‐energy‐density ASSLBs.

Deng, Tao [Department of Chemical and Biomolecular↗

A Universal Design of Lithium Anode via Dynamic Stability Strategy for Practical All‐Solid‐State Batteries

Abstract All‐solid‐state Li‐metal battery (ASSLB) chemistry with thin solid‐state electrolyte (SSE) membranes features high energy density and intrinsic safety but suffers from severe dendrite formation and poor interface contact during cycling, which hampers the practical application of rechargeable ASSLB. Here, we propose a universal design of thin Li‐metal anode (LMA) via a dynamic stability strategy to address these issues. The ultra‐thin LMA (20 μm) is in situ constructed with uniform highly Li‐ion conductive solid‐electrolyte interphase and composite‐polymer interphase (CPI) via electroplating process. As a result, the passivation layer with poor Li‐ion conduction on Li anode can be dissolved and small surface resistance can be achieved due to the good compatibility of CPI to SSEs. The cycling of Li symmetric cell with Li 6 PS 5 Cl thin film electrolyte (<100 μm) shows a high critical current density of >2.0 mA cm −2 with excellent cycling stability at 1.0 mA cm −2 . The ASSLBs paring with Ni‐rich LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode demonstrated the feasibility of engineered LMA design by presenting good rate capability from 0.1 C to 1.0 C at room temperature, as well as long‐term cycling stability (81 % retention after 100 cycles). This work represents a general pathway to make thin dendrite‐free LMA available for high‐energy‐density ASSLBs.

Deng, Tao [Department of Chemical and Biomolecular↗

Anion modification for stable solid electrolyte interphase in anode-free lithium metal batteries

The durability of anode-free Li metal batteries is largely limited by the undesired Li plating/stripping irreversibility on the current collector due to the infinite volume change, uncontrollable Li dendrite growth, and continuous parasitic reactions between Li metal and the electrolyte. To address these challenges, the formation of a stable and robust solid electrolyte interphase (SEI) with high ionic conductivity and strong mechanical strength is critical. Here, we developed an advanced electrolyte by introducing LiNO 3 into the localized high concentration electrolyte (LHCE) with lithium bis(fluorosulfonyl)imide (LiFSI) salt, 1,2-dimethoxyethane (DME) solvent, and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TFTE) diluent to in situ construct a LiF and Li x N y O z co-enriched passivation layer on the Cu current collector. The synergetic effect of high mechanical strength of LiF and high ionic conductivity of Li x N y O z endows the Li metal anode with a high Coulombic efficiency (CE) of 99.35%. In conclusion, in anode-free Li metal pouch cell using LiFePO 4 (LFP) as a cathode holds an exceptionally improved capacity retention under the charging/discharging rate of 1/3 C, demonstrating great promise for developing dendrite-free and safe Li metal batteries.

25 ENERGY STORAGE↗

P2-Type Moisture-Stable and High-Voltage-Tolerable Cathodes for High-Energy and Long-Life Sodium-Ion Batteries

P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 represents a promising cathode for Na-ion batteries, but it suffers from severe structural degradation upon storing in a humid atmosphere and cycling at a high cutoff voltage. Here we propose an in situ construction to achieve simultaneous material synthesis and Mg/Sn cosubstitution of Na 0.67 Ni 0.33 Mn 0.67 O 2 via one-pot solid-state sintering. Here, the materials exhibit superior structural reversibility and moisture insensitivity. In-operando XRD reveals an essential correlation between cycling stability and phase reversibility, whereas Mg substitution suppressed the P2–O2 phase transition by forming a new Z phase, and Mg/Sn cosubstitution enhanced the P2–Z transition reversibility benefiting from strong Sn–O bonds. DFT calculations disclosed high chemical tolerance to moisture, as the adsorption energy to H 2 O was lower than that of the pure Na 0.67 Ni 0.33 Mn 0.67 O 2 . A representative Na 0.67 Ni 0.23 Mg 0.1 Mn 0.65 Sn 0.02 O 2 cathode exhibits high reversible capacities of 123 mAh g –1 (10 mA g –1 ), 110 mAh g –1 (200 mA g –1 ), and 100 mAh g –1 (500 mA g –1 ) and a high capacity retention of 80% (500 mA g –1 , 500 cycles).

25 ENERGY STORAGE↗