Structurally engineered solvent-free LiFePO4 electrodes via hot-pressing with efficient ion transport pathways for lithium extraction from brine

Capacitive deionization is an attractive approach to water desalination and treatment. To achieve efficient capacitative desalination, rationally designed electrodes with high specific capacitances, conductivities, and stabilities are necessary. Here we report the construction of a three-dimensional (3D) holey graphene hydrogel (HGH). This material contains abundant in-plane pores, offering efficient ion transport pathways. Furthermore, it forms a highly interconnected network of graphene sheets, providing efficient electron transport pathways, and its 3D hierarchical porous structure can provide a large specific surface area for the adsorption and storage of ions. Consequently, HGH serves as a binder-free electrode material with excellent electrical conductivity. Cyclic voltammetry (CV) measurements indicate that the optimized HGH can achieve specific capacitances of 358.4 F·g−1 in 6 M KOH solution and 148 F·g−1 in 0.5 M NaCl solution. Because of these high capacitances, HGH has a desalination capacity as high as 26.8 mg·g−1 (applied potential: 1.2 V; initial NaCl concentration: ~5,000 mg·L−1).

Building stable and efficient electron and ion transport pathways are critically important for energy storage electrode materials and systems. Herein, a scallop-inspired shell engineering strategy is proposed and demonstrated to confine high volume change silicon microparticles toward the construction of stable and high volumetric capacity binder-free lithium battery anodes. As for each silicon microparticle, the methodology involves an inner sealed but adaptable overlapped graphene shell, and an outer open hollow shell consisting of interconnected reduced graphene oxide, mimicking the scallop structure. The inner closed shell enables simultaneous stabilization of the interfaces of silicon with both carbon and electrolyte, substantially facilitates efficient and rapid transport of both electrons and lithium ions from/to silicon, the outer open hollow shell creates stable and robust transport paths of both electrons and lithium ions throughout the electrode without any sophisticated additives. The resultant self-supported electrode has achieved stable cycling with rapidly increased coulombic efficiency in the early stage, superior rate capability, and remarkably high volumetric capacity upon a facile pressing process. The rational design and engineering of graphene shells of the silicon microparticles developed can provide guidance for the development of a wide range of other high capacity but large volume change electrochemically active materials.

Unveiling the ion transport mechanism to design and explore efficient and stable ion transport pathways for high‐performance transition metal oxide (TMO)−based electrochromic materials is highly desired yet challenging. Herein, this study has demonstrated that the interlayer spacing of layered vanadium penoxide (V2O5) films can be tuned by inserting different amounts of lithium−ion (Li+) within host V2O5 material, as well as adjusting ion transport behavior and electrochromic performance. These results show that V2O5 with a small amount of ion insertion delivers a stable ion transport process and electrochromic properties. Increasing the amount of inserted Li+ will enlarge the interlayer spacing, which provides abundant active sites and efficient ion transport channels, and thus reversible and rich color variation of yellow−green−blue−olive green−orange is realized. Nevertheless, an excess of ion insertion results in the crystal structure collapse and cyclic stability degradation. These findings give a rationale for the evolution of electrochromic properties during different electrochemical reaction stages. This work provides considerable insight into the ion transport behavior within the layered V2O5 films, which gives fundamental theoretical guidance for developing and designing superior layered TMO electrochromic materials.

Efficient transport pathways for ozone depleting very short-lived substances (VSLS) from their source regions into the stratosphere are a matter of current scientific debate, however they have yet to be fully identified on an observational basis. Understanding the increasing impact of chlorine containing VSLS (Cl-VSLS) on stratospheric ozone depletion is important in order to validate and improve model simulations and future predictions. We report on the first transport study using airborne in situ measurements of the Cl-VSLS dichloromethane (CH2Cl2) and trichloromethane (chloroform, CHCl3) to derive a detailed description of the two most efficient and fast transport pathways from (sub-)tropical source regions into the extratropical lower stratosphere (Ex-LS) in northern hemisphere (NH) late summer. The Cl-VSLS measurements were obtained in the upper troposphere and lower stratosphere (UTLS) above Western Europe and the mid latitude Atlantic Ocean in the frame of the WISE (Wave-driven ISentropic Exchange) aircraft campaign in autumn 2017 and are combined with the results from a three-dimensional simulation of a Lagrangian transport model as well as back-trajectory calculations. Compared to background measurements of similar age we find up to 150 % enhanced CH2Cl2 and up to 100 % enhanced CHCl3 mixing ratios in the Ex-LS. We link the measurements of enhanced mixing ratios to emissions in the region of southern and eastern Asia. Transport from this area to the Ex-LS at potential temperatures in the range of 370–400 K takes about 5–10 weeks via the Asian summer monsoon anticyclone (ASMA). Our measurements suggest anthropogenic sources to be the cause of these strongly elevated Cl-VSLS concentrations observed at the top of the lowermost stratosphere (LMS). A faster transport pathway into the Ex-LS is derived from particularly low CH2Cl2 and CHCl3 mixing ratios in the UTLS. These low mixing ratios reflect weak emission sources and a local seasonal minimum of both species in the boundary layer of Central America and the tropical Atlantic. We show that air masses uplifted by hurricanes, the North American monsoon, and general convection above Central America into the tropical tropopause layer to potential temperatures of about 360–370 K are transported isentropically within 1–5 weeks into the Ex-LS. This transport pathway linked to the North American monsoon mainly impacts the middle and lower part of the LMS with particularly low CH2Cl2 and CHCl3 mixing ratios. In a case study, we specifically analyze air samples directly linked to the uplift by the category 5 hurricane Maria that occurred during October 2017 above the Atlantic Ocean. Regionally differing CHCl3 : CH2Cl2 emission ratios derived from our UTLS measurements suggest a clear similarity between CHCl3 and CH2Cl2 when emitted by anthropogenic sources and differences between the two species mainly caused by additional, likely biogenic, CHCl3 sources. Overall, the transport of strongly enhanced CH2Cl2 and CHCl3 mixing ratios from southern and eastern Asia via the ASMA is the main factor for increasing the chlorine loading from the analyzed VSLS in the Ex-LS during NH late summer. Thus, further increases in Asian CH2Cl2 and CHCl3 emissions, as frequently reported in recent years, will further increase the impact of Cl-VSLS on stratospheric ozone depletion.

<strong class="journal-contentHeaderColor">Abstract.</strong> <span id="page2050"/>Efficient transport pathways for ozone-depleting very short-lived substances (VSLSs) from their source regions into the stratosphere are a matter of current scientific debate; however they have yet to be fully identified on an observational basis. Understanding the increasing impact of chlorine-containing VSLSs (Cl-VSLSs) on stratospheric ozone depletion is important in order to validate and improve model simulations and future predictions. We report on a transport study using airborne in situ measurements of the Cl-VSLSs dichloromethane (CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span>) and trichloromethane (chloroform, CHCl<span class="inline-formula">₃</span>) to derive a detailed description of two transport pathways from (sub)tropical source regions into the extratropical upper troposphere and lower stratosphere (Ex-UTLS) in the Northern Hemisphere (NH) late summer. The Cl-VSLS measurements were obtained in the upper troposphere and lower stratosphere (UTLS) above western Europe and the midlatitude Atlantic Ocean in the frame of the WISE (Wave-driven ISentropic Exchange) aircraft campaign in autumn 2017 and are combined with the results from a three-dimensional simulation of a Lagrangian transport model as well as back-trajectory calculations. Compared to background measurements of similar age we find up to <span class="inline-formula">150</span> % enhanced CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span> and up to <span class="inline-formula">100</span> % enhanced CHCl<span class="inline-formula">₃</span> mixing ratios in the extratropical lower stratosphere (Ex-LS). We link the measurements of enhanced CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span> and CHCl<span class="inline-formula">₃</span> mixing ratios to emissions in the region of southern and eastern Asia. Transport from this area to the Ex-LS at potential temperatures in the range of 370–400 K takes about 6–11 weeks via the Asian summer monsoon anticyclone (ASMA). Our measurements suggest anthropogenic sources to be the cause of these strongly elevated Cl-VSLS concentrations observed at the top of the lowermost stratosphere (LMS). A faster transport pathway into the Ex-LS is derived from particularly low CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span> and CHCl<span class="inline-formula">₃</span> mixing ratios in the UTLS. These low mixing ratios reflect weak emissions and a local seasonal minimum of both species in the boundary layer of Central America and the tropical Atlantic. We show that air masses uplifted by hurricanes, the North American monsoon, and general convection above Central America into the tropical tropopause layer to potential temperatures of about 360–370 K are transported isentropically within 5–9 weeks from the boundary layer into the Ex-LS. This transport pathway linked to the North American monsoon mainly impacts the middle and lower part of the LMS with particularly low CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span> and CHCl<span class="inline-formula">₃</span> mixing ratios. In a case study, we specifically analyze air samples directly linked to the uplift by the Category 5 Hurricane Maria that occurred during October 2017 above the Atlantic Ocean. CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span> and CHCl<span class="inline-formula">₃</span> have similar atmospheric sinks and lifetimes, but the fraction of biogenic emissions is clearly higher for CHCl<span class="inline-formula">₃</span> than for the mainly anthropogenically emitted CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span>; consequently lower CHCl<span class="inline-formula">₃</span> : CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span> ratios are expected in air parcels showing a higher impact of anthropogenic emissions. The observed CHCl<span class="inline-formula">₃</span> : CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span> ratio suggests clearly stronger anthropogenic emissions in the region of southern and eastern Asia compared to those in the region of Central America and the tropical Atlantic. Overall, the transport of strongly enhanced CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span> and CHCl<span class="inline-formula">₃</span> mixing ratios from southern and eastern Asia via the ASMA is the main factor in increasing the chlorine loading from the analyzed VSLSs in the Ex-LS during the NH late summer. Thus, further increases in Asian CH<span class="inline-formula">₂</span>Cl<span class="inline-formula">₂</span> and CHCl<span class="inline-formula">₃</span> emissions, as frequently reported in recent years, will further increase the impact of Cl-VSLSs on stratospheric ozone depletion.

Efficient transport pathways for ozone depleting very short-lived substances (VSLS) from their source regions into the stratosphere are a matter of current scientific debate, however they have yet to be fully identified on an observational basis. Understanding the increasing impact of chlorine containing VSLS (Cl-VSLS) on stratospheric ozone depletion is important in order to validate and improve model simulations and future predictions. We report on the first transport study using airborne in situ measurements of the Cl-VSLS dichloromethane (CH2Cl2) and trichloromethane (chloroform, CHCl3) to derive a detailed description of the two most efficient and fast transport pathways from (sub-)tropical source regions into the extratropical lower stratosphere (Ex-LS) in northern hemisphere (NH) late summer. The Cl-VSLS measurements were obtained in the upper troposphere and lower stratosphere (UTLS) above Western Europe and the mid latitude Atlantic Ocean in the frame of the WISE (Wave-driven ISentropic Exchange) aircraft campaign in autumn 2017 and are combined with the results from a three-dimensional simulation of a Lagrangian transport model as well as back-trajectory calculations. Compared to background measurements of similar age we find up to 150 % enhanced CH2Cl2 and up to 100 % enhanced CHCl3 mixing ratios in the Ex-LS. We link the measurements of enhanced mixing ratios to emissions in the region of southern and eastern Asia. Transport from this area to the Ex-LS at potential temperatures in the range of 370–400 K takes about 5–10 weeks via the Asian summer monsoon anticyclone (ASMA). Our measurements suggest anthropogenic sources to be the cause of these strongly elevated Cl-VSLS concentrations observed at the top of the lowermost stratosphere (LMS). A faster transport pathway into the Ex-LS is derived from particularly low CH2Cl2 and CHCl3 mixing ratios in the UTLS. These low mixing ratios reflect weak emission sources and a local seasonal minimum of both species in the boundary layer of Central America and the tropical Atlantic. We show that air masses uplifted by hurricanes, the North American monsoon, and general convection above Central America into the tropical tropopause layer to potential temperatures of about 360–370 K are transported isentropically within 1–5 weeks into the Ex-LS. This transport pathway linked to the North American monsoon mainly impacts the middle and lower part of the LMS with particularly low CH2Cl2 and CHCl3 mixing ratios. In a case study, we specifically analyze air samples directly linked to the uplift by the category 5 hurricane Maria that occurred during October 2017 above the Atlantic Ocean. Regionally differing CHCl3 : CH2Cl2 emission ratios derived from our UTLS measurements suggest a clear similarity between CHCl3 and CH2Cl2 when emitted by anthropogenic sources and differences between the two species mainly caused by additional, likely biogenic, CHCl3 sources. Overall, the transport of strongly enhanced CH2Cl2 and CHCl3 mixing ratios from southern and eastern Asia via the ASMA is the main factor for increasing the chlorine loading from the analyzed VSLS in the Ex-LS during NH late summer. Thus, further increases in Asian CH2Cl2 and CHCl3 emissions, as frequently reported in recent years, will further increase the impact of Cl-VSLS on stratospheric ozone depletion.

Efficient transport pathways for ozone depleting very short-lived substances (VSLS) from their source regions into the stratosphere are a matter of current scientific debate, however they have yet to be fully identified on an observational basis. Understanding the increasing impact of chlorine containing VSLS (Cl-VSLS) on stratospheric ozone depletion is important in order to validate and improve model simulations and future predictions. We report on the first transport study using airborne in situ measurements of the Cl-VSLS dichloromethane (CH2Cl2) and trichloromethane (chloroform, CHCl3) to derive a detailed description of the two most efficient and fast transport pathways from (sub-)tropical source regions into the extratropical lower stratosphere (Ex-LS) in northern hemisphere (NH) late summer. The Cl-VSLS measurements were obtained in the upper troposphere and lower stratosphere (UTLS) above Western Europe and the mid latitude Atlantic Ocean in the frame of the WISE (Wave-driven ISentropic Exchange) aircraft campaign in autumn 2017 and are combined with the results from a three-dimensional simulation of a Lagrangian transport model as well as back-trajectory calculations. Compared to background measurements of similar age we find up to 150 % enhanced CH2Cl2 and up to 100 % enhanced CHCl3 mixing ratios in the Ex-LS. We link the measurements of enhanced mixing ratios to emissions in the region of southern and eastern Asia. Transport from this area to the Ex-LS at potential temperatures in the range of 370–400 K takes about 5–10 weeks via the Asian summer monsoon anticyclone (ASMA). Our measurements suggest anthropogenic sources to be the cause of these strongly elevated Cl-VSLS concentrations observed at the top of the lowermost stratosphere (LMS). A faster transport pathway into the Ex-LS is derived from particularly low CH2Cl2 and CHCl3 mixing ratios in the UTLS. These low mixing ratios reflect weak emission sources and a local seasonal minimum of both species in the boundary layer of Central America and the tropical Atlantic. We show that air masses uplifted by hurricanes, the North American monsoon, and general convection above Central America into the tropical tropopause layer to potential temperatures of about 360–370 K are transported isentropically within 1–5 weeks into the Ex-LS. This transport pathway linked to the North American monsoon mainly impacts the middle and lower part of the LMS with particularly low CH2Cl2 and CHCl3 mixing ratios. In a case study, we specifically analyze air samples directly linked to the uplift by the category 5 hurricane Maria that occurred during October 2017 above the Atlantic Ocean. Regionally differing CHCl3 : CH2Cl2 emission ratios derived from our UTLS measurements suggest a clear similarity between CHCl3 and CH2Cl2 when emitted by anthropogenic sources and differences between the two species mainly caused by additional, likely biogenic, CHCl3 sources. Overall, the transport of strongly enhanced CH2Cl2 and CHCl3 mixing ratios from southern and eastern Asia via the ASMA is the main factor for increasing the chlorine loading from the analyzed VSLS in the Ex-LS during NH late summer. Thus, further increases in Asian CH2Cl2 and CHCl3 emissions, as frequently reported in recent years, will further increase the impact of Cl-VSLS on stratospheric ozone depletion.

Facilitated belt for ion transport by comb-shape Poly(terphenyl piperidone) carried with macrocyclic crown ether as anchor in anion exchange membrane

Three-dimensional N- and S-codoped graphene hydrogel with in-plane pores for high performance supercapacitor

Improved NO2 gas sensing performance of nanoporous conjugated polymer (CP) thin films by incorporating preformed CP nanowires

Fast charge rate supercapacitors based on nitrogen-doped aligned carbon nanosheet networks

CoFe2O4/carbon nanotube aerogels as high performance anodes for lithium ion batteries

Mixed ionic-electronic conductors have great potential as materials for energy storage applications. However, despite their promising properties, only a handful of metal-organic frameworks (MOFs) provide efficient pathways for both ion and electron transport. This work reports a proton-electron dual-conductive MOF based on tetrathiafulvalene(TTF)-phosphonate linkers and lanthanum ions. The formation of regular, partially oxidized TTF stacks with short S···S interactions facilitates electron transport via a hopping mechanism, reporting a room-temperature conductivity of 7.2 × 10-6 S cm-1. Additionally, the material exhibits a proton conductivity of 4.9 × 10-5 S cm-1 at 95% relative humidity conditions due to the presence of free -POH groups, enabling efficient proton transport pathways. These results demonstrate the potential of integrating electroactive building blocks along with phosphonate groups toward the development of mixed ionic-electronic conductors.

An oriented strategy to build efficient intrinsic proton transport pathways in MOF-808 by functionalizing the MOF skeleton has been proposed.

The synthesis of layered double hydroxide (LDH) as electroactive material has been well reported; however, fabricating an LDH electrode with excellent electrochemical performance at high current density remains a challenge. In this paper, we report a 3D hierarchical porous flower-like NiAl-LDH grown on nickel foam (NF) through a liquid-phase deposition method as a high-performance binder-free electrode for energy storage. With large ion-accessible surface area as well as efficient electron and ion transport pathways, the prepared LDH-NF electrode achieves high specific capacity (1250 C g-1 at 2 A g-1 and 401 C g-1 at 50 A g-1) after 5000 cycles of activation at 20 A g-1 and high cycling stability (76.7% retention after another 5000 cycles at 50 A g-1), which is higher than those of most previously reported NiAl-LDH-based materials. Moreover, a hybrid supercapacitor with LDH-NF as the positive electrode and porous graphene nanosheet coated on NF (GNS-NF) as the negative electrode, delivers high energy density (30.2 Wh kg-1 at a power density of 800 W kg-1) and long cycle life, which outperforms the other devices reported in the literature. This study shows that the prepared LDH-NF electrode offers great potential in energy storage device applications. Figure 1