Electrochemically Dealloyed 3D Porous Copper Nanostructure as Anode Current Collector of Li-Metal Batteries.

The commercialization of high-energy Li-metal batteries is impeded by Li dendrites formed during electrochemical cycling and the safety hazards it causes. Here, a novel porous copper current collector that can effectively mitigate the dendritic growth of Li is reported. This porous Cu foil is fabricated via a simple two-step electrochemical process, where Cu-Zn alloy is electrodeposited on commercial copper foil and then Zn is electrochemically dissolved to form a 3D porous structure of Cu. The 3D porous Cu layers on average have a thickness of ≈14 um and porosity of ≈72%. This current collector can effectively suppress Li dendrites in cells cycled with a high areal capacity of 10 mAh cm-2 and under a high current density of 10 mA cm-2 . This electrochemical fabrication method is facile and scalable for mass production. Results of advanced in situ synchrotron X-ray diffraction reveal the phase evolution of the electrochemical deposition and dealloying processes.

Green Approach for Rare Earth Element (REE) Recovery from Coal Fly Ash.

Due to the growing demands of rare earth elements (REEs) and the vulnerability of REEs to potential supply disruption, there have been increasing interests in recovering REEs from waste streams such as coal fly ash (CFA). Meanwhile, CFA as a large industrial waste stream in the United States (U.S.) poses significant environmental and economic burdens. Recovery of REEs from CFA is a promising solution to the REE scarcity issue and also brings opportunities for CFA management. This study demonstrates a green system for REE recovery from Class F and C CFA that consists of three modules: REE leaching using citrate, REE separation and concentration using oxalate, and zeolite synthesis using secondary wastes from Modules I and II. In Module I, ∼10 and 60% REEs were leached from the Class F and C CFA samples, respectively, using citrate at pH 4. In Module II, the addition of oxalate selectively precipitated and concentrated REEs from the leachate via the formation of weddellite (CaC2O4·2H2O), while other trace metals remained in solution. In Module III, zeolite was synthesized using wastes from Modules I and II. This study is characterized by the successful recovery of REEs and upcycling of secondary wastes, which addresses both REE recovery and CFA management challenges.

A comprehensive assessment of runoff dynamics in response to climate change and human activities in a typical karst watershed, southwest China.

The Chengbi River Basin is a typical karst watershed in Southwest China. Understanding the effects of climate change (CC) and human activities (HAs) on hydrological process is important for regional water resources management and water security. However, a comprehensive assessment of the effects of CC and HAs on runoff dynamics at different time scales in the Chengbi River Basin is still lacking. To address these needs, we used Budyko Mezentsev-Choudhurdy-Yang and Slope change ratio of accumulative quantity methods to assess the contribution of the changing environment to annual and intra-annual runoff changes in the Chengbi River Basin. The results indicated that annual runoff time series was divided into the base phase Ta (1980-1996) and the change phase Tb (1997-2019). Compared to the natural status in Ta, the relative contributions of CC and HAs to the runoff increase in Tb were 154.86% and -54.86%. In addition, the shift in intra-annual runoff occurred in 2007 and was mainly caused by HAs, with a contribution rate of 76.22%. The increase in annual runoff in Tb could be attributed to the positive contribution of rainfall. Changes in rainfall and reservoir construction altered the original state of intra-annual runoff. Furthermore, the high degree of heterogeneity in the surface karst zone increased the runoff coefficient. The spatial unsaturation of the subsurface water-bearing media and rainfall patterns caused a significant lag effect in the response of surface runoff to rainfall. This study can help researchers and policy makers to better understand the response of karst runoff to changing environment and provide insights for future water resources management and flood control measures.

Redox Cycling Driven Transformation of Layered Manganese Oxides to Tunnel Structures.

Mn oxides are among the most ubiquitous minerals on Earth and play critical roles in numerous elemental cycles in biotic/abiotic loops as the key redox center. Yet, it has long puzzled geochemists why the laboratory synthesis of todorokite, a tunnel-structured Mn oxide, is extremely difficult while it is the dominant form over other tunneled phases in low-temperature natural environments. This study employs a novel electrochemical method to mimic the cyclic redox reactions occurring over long geological time scales in an accelerated manner. The results revealed that the kinetics and electron flux of the cyclic redox reaction are key to the layer-to-tunnel structure transformation of Mn oxides, provided new insights for natural biotic and abiotic redox reactions, and explained the dominance of todorokite in nature.

Lithium-Doping Stabilized High-Performance P2-Na0.66Li0.18Fe0.12Mn0.7O2 Cathode for Sodium Ion Batteries.

While sodium-ion batteries (SIBs) hold great promise for large-scale electric energy storage and low speed electric vehicles, the poor capacity retention of the cathode is one of the bottlenecks in the development of SIBs. Following a strategy of using lithium doping in the transition-metal layer to stabilize the desodiated structure, we have designed and successfully synthesized a novel layered oxide cathode P2-Na0.66Li0.18Fe0.12Mn0.7O2, which demonstrated a high  capacity of 190 mAh g-1 and a remarkably high capacity retention of ∼87% after 80 cycles within a wide voltage range of 1.5-4.5 V. The outstanding stability is attributed to the reversible migration of lithium during cycling and the elimination of the detrimental P2-O2 phase transition, revealed by ex situ and in situ X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy.

Investigation into the energy storage behaviour of layered α-V2O5 as a pseudo-capacitive electrode using operando Raman spectroscopy and a quartz crystal microbalance.

α-V2O5 nanowires with a layered structure have been fabricated through a two-step procedure. When measured as a pseudo-capacitive electrode with a three-electrode configuration in 1 M Na2SO4 aqueous solutions, α-V2O5 exhibits ideal capacitive characteristics with a specific capacitance of ∼238 F g-1 at a high current of 2 A g-1, but poor cycling stability with a continuous drop in the first 2000 cycles before it is maintained. To find possible solutions towards this problem, the energy storage behavior of the α-V2O5 electrode has been carefully investigated. In situ Raman analysis suggests that it is electrolytic hydrated cations [Na(H2O)n]+ rather than anions (SO42-) that are involved in the energy storage process through reversible adsorption/desorption on the surface or intercalation/deintercalation at the interlayer of the (001) planes accompanied by interlayer spacing expansion/contraction. Moreover, the electrochemical quartz crystal microbalance results indicate that, besides a reversible mass change, there is a continuous mass loss that may originate from slow dissolution of V2O5, which should bear the main responsibility for the poor stability (initial dramatic drop). Hence, how to inhibit dissolution, such as by coating or adding additives in the electrolyte, is found to be the key approach to improve the stability of V2O5 based electrodes.

Development and Recent Progress of Hoses for Cryogenic Liquid Transportation.

Recently, the application of cryogenic hoses in the field of cryogenic media has become a hot topic, especially in the industry of offshore liquefied natural gas and aerospace field. However, the structure of cryogenic hoses is complex, and reasonable structural properties are required due to the harsh working conditions. There is still plenty of scope for further development to improve the performance in all aspects. In this paper, the current development status of cryogenic hoses for liquefied natural gas (LNG) transportation is reviewed first, including the types, manufacturers, structural forms, performance, and key technical challenges. And then, the recent progress and prospect of cryogenic hoses for cryogenic liquid transportation (such as LNG and liquid oxygen) are summarized, including structure design, low-temperature resistant polymers, liquid oxygen compatible polymers, and leakage monitoring technologies. This paper provides a comprehensive overview of the research development and application of cryogenic hoses. Moreover, future research directions have been proposed to facilitate its practical applications in aerospace.

High-Entropy Engineering of Cubic SiP with Metallic Conductivity for Fast and Durable Li-Ion Batteries.

A cost-effective, scalable ball milling process is employed to synthesize the InGeSiP3 compound with a cubic ZnS structure, aiming to address the sluggish reaction kinetics of Si-based anodes for Lithium-ion batteries. Experimental measurements and first-principles calculations confirm that the synthesized InGeSiP3 exhibits significantly higher electronic conductivity, larger Li-ion diffusivity, and greater tolerance to volume change than its parent phases InGe (or Si)P2 or In (or Ge, or Si)P. These improvements stem from its elevated configurational entropy. Multiple characterizations validate that InGeSiP3 undergoes a reversible Li-storage mechanism that involves intercalation, followed by conversion and alloy reactions, resulting in a reversible capacity of 1733 mA h g-1 with an initial Coulombic efficiency of 90%. Moreover, the InGeSiP3-based electrodes exhibit exceptional cycling stability, retaining an 1121 mA h g-1 capacity with a retention rate of ≈87% after 1500 cycles at 2000 mA g-1 and remarkable high-rate capability, achieving 882 mA h g-1 at 10 000 mA g-1. Inspired by the distinctive characteristic of high entropy, the synthesis is extended to high entropy GaCu (or Zn)InGeSiP5, CuZnInGeSiP5, GaCuZnInGeSiP6, InGeSiP2S (or Se), and InGeSiPSSe. This endeavor overcomes the immiscibility of different metals and non-metals, paving the way for the electrochemical energy storage application of high-entropy silicon-phosphides.

Conformal Coating of a High-Voltage Spinel to Stabilize LiCoO2 at 4.6 V.

The ever-growing demand for portable electronic devices has put forward higher requirements on the energy density of layered LiCoO2 (LCO). The unstable surface structure and side reactions with electrolytes at high voltages (>4.5 V) however hinder its practical applications. Here, considering the high-voltage stability and three-dimensional lithium-ion transport channel of the high-voltage Li-containing spinel (M = Ni and Co) LiMxMn2-xO4, we design a conformal and integral LiNixCoyMn2-x-yO4 spinel coating on the surface of LCO via a sol-gel method. The accurate structure of the coating layer is identified to be a spinel solid solution with gradient element distribution, which compactly covers the LCO particle. The coated LCO exhibits significantly improved cycle performance (86% capacity remained after 100 cycles at 0.5C in 3-4.6 V) and rate performance (150 mAh/g at a high rate of 5C). The characterizations of the electrodes from the bulk to surface suggest that the conformal spinel coating acts as a physical barrier to inhibit the side reactions and stabilize the cathode-electrolyte interface (CEI). In addition, the artificially designed spinel coating layer is well preserved on the surface of LCO after prolonged cycling, preventing the formation of an electrochemically inert Co3O4 phase and ensuring fast lithium transport kinetics. This work provides a facile and effective method for solving the surface problems of LCO operated at high voltages.

Raising the Intrinsic Safety of Layered Oxide Cathodes by Surface Re-Lithiation with LLZTO Garnet-Type Solid Electrolytes.

Battery safety concerns are becoming more and more prominent with the increasing demands of lithium-ion batteries (LIBs) with higher energy density. The greatest threat to battery safety derives from the easy release of oxygen from the high-capacity layered oxide cathodes at highly delithiated states and subsequent exothermic reactions with reductive agents in batteries. Herein, it is demonstrated that solid electrolyte Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZTO) can supply lithium ions to re-lithiate the charged LiCoO2 at elevated temperatures. Such a re-lithiation process can lower the state-of-charge of LiCoO2 , and thus, inherently postpones its structural decomposition and the associated release of oxygen during the heating process. The LiCoO2 /graphite full cell with 1 wt% addition of LLZTO demonstrates remarkably enhanced safety performances. This work proposes a strategy that through the adoption of solid electrolytes to solve safety issues raised from both flammable liquid electrolytes and high capacity cathodes, to achieve intrinsically safe LIBs or solid-state batteries.

Multiprincipal Component P2-Na0.6(Ti0.2Mn0.2Co0.2Ni0.2Ru0.2)O2 as a High-Rate Cathode for Sodium-Ion Batteries.

Mixing transition metal cations in nearly equiatomic proportions in layered oxide cathode materials is a new strategy for improving the performances of Na-ion batteries. The mixing of cations not only offers entropic stabilization of the crystal structure but also benefits the diffusion of Na ions with tuned diffusion activation energy barriers. In light of this strategy, a high-rate Na0.6(Ti0.2Mn0.2Co0.2Ni0.2Ru0.2)O2 cathode was designed, synthesized, and investigated, combining graph-based deep learning calculations and complementary experimental characterizations. This new cathode material delivers high discharge capacities of 164 mA g-1 at 0.1 C and 68 mAh g-1 at a very high rate of 86 C, demonstrating an outstanding high rate capability. Ex situ and operando synchrotron X-ray diffraction were used to reveal the detailed structural evolution of the cathode upon cycling. Using the climbing-image nudged elastic-band calculation and Ab initio molecular dynamics simulations, we show that the optimal transition metal composition enables a percolating network of low barrier pathways for fast, macroscopic Na diffusion, resulting in the observed high rate performance.

Data for ultimate bearing capacity of concrete-filled steel tubular members and arches by the elastic modulus reduction method.

Homogeneous generalized yield function is adopted in this article to calculate the ultimate bearing capacity of 93 concrete-filled steel tubular components with detailed test data, and the ratios of the ultimate bearing capacity calculated to the tested are presented. Moreover, the incremental nonlinear finite element method and elastic modulus reduction method are adopted to evaluate the ultimate bearing capacity of 11 concrete-filled steel tubular arches, 7 among which with detailed test data. The component data cover those under different loading conditions, material strength and geometric parameters, and the arch data include those under different loading conditions and rise to span ratios. The data provided are useful to investigate the strength of CFST members and arches and to demonstrate the validation of other numerical methods. The current data are considered as a complementary for the main work "Linear elastic iteration technique for ultimate bearing capacity of circular CFST arches" [1].

A stabilized PEO-based solid electrolyte via a facile interfacial engineering method for a high voltage solid-state lithium metal battery.

A facile interfacial engineering method via in situ electro-deposition was developed to stabilize the PEO-based solid electrolyte in high voltage solid-state lithium metal batteries (Li/PEO-LiTFSI/LiNi0.5Co0.2Mn0.3O2), which demonstrate a superior capacity retention of 72.3% after 200 cycles in 3.0-4.2 V. The critical factors for the interfacial engineering method were also demonstrated in this study.

Enhanced Electrochemical Performance of the Lithium-Manganese-Rich Cathode for Li-Ion Batteries with Na and F CoDoping.

The lithium-manganese-rich layered oxide cathode (LMR-NMC), xLi2MnO3·(1 - x)LiMO2 (M = Co, Ni, and Mn), is on demand because of its high specific capacity of over 250 mA h g-1 between the voltage range 2.0-4.8 V (vs Li/Li+). Because of the requirement of activating the Li2MnO3 phase in the first cycle, oxygen extraction from the lattice structure occurs. Consequently, capacity fading and voltage fading during cycling are still major obstacles to the commercialization of LMR-NMC in battery applications. Here, codoping Na and F into LMR-NMC via facile hydroxide coprecipitation followed by solid-state reaction is introduced. Na and F are partially substituted into Li and O sites, respectively. These dopant ions enlarge the Li slab, which in turn eases Li diffusion and minimizes oxygen loss, thereby stabilizing the structure. The codoped sample exhibits both high capacity retention (97%) and high voltage retention (91%) over 100 cycles with an initial discharge capacity of 260 mA h g-1 at 0.1 C. Compared to other reports on LMR-NMC as obtained by coprecipitation, results from this study show the best capacity retention. The developed codoping approach may provide a new strategy for designing high-performance LMR-NMC cathodes for next-generation lithium ion batteries.

Fast Energy Storage in Two-Dimensional MoO2 Enabled by Uniform Oriented Tunnels.

While pseudocapacitive electrodes have potential to store more energy than electrical double-layer capacitive electrodes, their rate capability is often limited by the sluggish kinetics of the Faradaic reactions or poor electronic and ionic conductivity. Unlike most transition-metal oxides, MoO2 is a very promising material for fast energy storage, attributed to its unusually high electronic and ionic conductivity; the one-dimensional tunnel is ideally suited for fast ionic transport. Here we report our findings in preparation and characterization of ultrathin MoO2 sheets with oriented tunnels as a pseudocapacitive electrode for fast charge storage/release. A composite electrode consisting of MoO2 and 5 wt % GO demonstrates a capacity of 1097 C g-1 at 2 mV s-1 and 390 C g-1 at 1000 mV s-1 while maintaining ∼80% of the initial capacity after 10,000 cycles at 50 mV s-1, due to minimal change in structural features of the MoO2 during charge/discharge, except a small volume change (∼14%), as revealed from operando Raman spectroscopy, X-ray analyses, and density functional theory calculations. Further, the volume change during cycling is highly reversible, implying high structural stability and long cycling life.

Porous Functionalized Self-Standing Carbon Fiber Paper Electrodes for High-Performance Capacitive Energy Storage.

A facile and cost-efficient approach to functionalize raw carbon fiber paper (CFP) used for a self-standing capacitive electrode has been proposed here. Benefiting from the improved specific surface area and surface functional groups, the functionalized CFP (F-CFP) showed much enhanced capacitive performance, 3 orders of magnitude higher than that of the raw CFP. It delivered the areal capacitance of 1275 mF cm-2 at 5 mA cm-2 with a rather wide voltage window of 1.4 V (-0.4 to 1 V vs Ag/AgCl) in 0.5 M H2SO4. However, in a neutral 1 M Na2SO4 aqueous solution, although the areal capacitance of 1115 mF cm-2 at 3 mA cm-2 is slightly smaller, the potential window is much wider (2 V, -1 to 1 V vs Ag/AgCl), indicating a high overpotential of hydrogen evolution. The areal capacitance was still as high as 722 mF cm-2 at a very fast charge-discharge current density of 50 mA cm-2, and about 66% of the initial capacitance (at 3 mA cm-2) was remained in Na2SO4, indicating considerable rate capability.

Synthesis and Characterization of Self-Standing and Highly Flexible δ-MnO2@CNTs/CNTs Composite Films for Direct Use of Supercapacitor Electrodes.

Self-standing and flexible films worked as pseudocapacitor electrodes have been fabricated via a simple vacuum-filtration procedure to stack δ-MnO2@carbon nanotubes (CNTs) composite layer and pure CNT layer one by one with CNT layers ended. The lightweight CNTs layers served as both current collector and supporter, while the MnO2@CNTs composite layers with birnessite-type MnO2 worked as active layer and made the main contribution to the capacitance. At a low discharge current of 0.2 A g(-1), the layered films displayed a high areal capacitance of 0.293 F cm(-2) with a mass of 1.97 mg cm(-2) (specific capacitance of 149 F g(-1)) and thickness of only 16.5 µm, and hence an volumetric capacitance of about 177.5 F cm(-3). Moreover, the films also exhibited a good rate capability (only about 15% fading for the capacitance when the discharge current increased to 5 A g(-1) from 0.2 A g(-1)), outstanding cycling stability (about 90% of the initial capacitance was remained after 5,000 cycles) and high flexibility (almost no performance change when bended to different angles). In addition, the capacitance of the films increased proportionally with the stacked layers and the geometry area. E.g., when the stacked layers were three times many with a mass of 6.18 mg cm(-2), the areal capacitance of the films was increased to 0.764 F cm(-2) at 0.5 A g(-1), indicating a high electronic conductivity. It is not overstated to say that the flexible and lightweight layered films emerged high potential for future practical applications as supercapacitor electrodes.

Microtube bundle carbon derived from Paulownia sawdust for hybrid supercapacitor electrodes.

The structure and capacitive properties of microtube bundle carbons (MTBCs) from carbonization of paulownia sawdust (PS) followed by NaOH activation were investigated. Morphology analyses indicated that MTBCs had abundant micropores and mesopores with a high specific surface area of about 1900 m(2) g(-1). Cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy studies demonstrated the excellent charge storage, transfer capability, and low impedance of MTBCs. The specific capacitance of MTBCs-4 was as high as 227 F g(-1) at 2 mV s(-1). Experimental results indicated that MTBCs provide smooth charge-transfer pathways for the ions in electrolytes and gateways to micropores and mesopores in the bulk. The hybrid supercapacitor model of MTBCs based on electrical double-layer capacitors and electrostatic capacitors was discussed and demonstrated. MTBCs are electrostatic capacitors at low frequency current, and may provide the pathways for easy accessibility of efficient charge transmission and high energy storage.

One-step preparation of nitrogen-doped graphene quantum dots from oxidized debris of graphene oxide.

Highly blue-luminescent nitrogen-doped graphene quantum dots (N-GQDs) are obtained by hydrothermal treatment of graphene oxide in the presence of ammonia. The yield of N-GQDs is about 8.7% in weight. A high quantum yield of maximum 24.6% at an excitation wavelength of 340 nm is achieved. They are applied for bioimaging of HeLa cells, and showed bright luminescence and excellent biocompatibility.