High Air Stability Research Articles

Reaction-driven restructuring of defective PtSe2 into ultrastable catalyst for the oxygen reduction reaction.

PtM (M = S, Se, Te) dichalcogenides are promising two-dimensional materials for electronics, optoelectronics and gas sensors due to their high air stability, tunable bandgap and high carrier mobility. However, their potential as electrocatalysts for the oxygen reduction reaction (ORR) is often underestimated due to their semiconducting properties and limited surface area from van der Waals stacking. Here we show an approach for synthesizing a highly efficient and stable ORR catalyst by restructuring defective platinum diselenide (DEF-PtSe2) through electrochemical cycling in an O2-saturated electrolyte. After 42,000 cycles, DEF-PtSe2 exhibited 1.3 times higher specific activity and 2.6 times higher mass activity compared with a commercial Pt/C electrocatalyst. Even after 126,000 cycles, it maintained superior ORR performance with minimal decay. Quantum mechanical calculations using hybrid density functional theory reveal that the improved performance is due to the synergistic contributions from Pt nanoparticles and the apical active sites on the DEF-PtSe2 surface. This work highlights the potential of DEF-PtSe2 as a durable electrocatalyst for ORR, offering insights into PtM dichalcogenide electrochemistry and the design of advanced catalysts.

Flexible and air-stable n-type oleylamine/carbon nanotube hybrid yarns for high-performance wearable thermoelectric generators

Wearable thermoelectric generators (TEGs), envisioned to harness the temperature gradient (ΔT) between the human body and the environment into electricity, hold great promise for powering wearable electronics. However, their practical application has been hampered by the scarcity of flexible n-type thermoelectric (TE) materials boasting both high performance and long-term air stability. Here, we introduce a significant advancement by developing an n-type TE material through immersing carbon nanotube yarn (CNTY) into an oleylamine (OAm)/ethanol solution, followed by drying under atmospheric conditions. The resulting OAm/CNTY exhibits a Seebeck coefficient of -80.48 μV K-1, an electrical conductivity of 1353.18 S cm-1 and a power factor of 876.25 μW m-1 K-2, all while exhibiting exceptional mechanical flexibility. Notably, this hybrid yarn maintains stable n-type behavior even after enduring exposure to air for over 370 days, surpassing previous n-type TE materials based on CNT fibers and CNTY. Leveraging this advancement, we construct a prototype wearable TEG by alternately embroidering pristine p-type CNTY and n-type OAm/CNTY into a polyester spacer fabric, electrically connecting them in series using conductive silver paint. The resulting wearable TEG, featuring with 150 p-n couples, yields an output voltage of 705.94 mV and a maximum output power of 44.34 μW at a ΔT of 40 K. This groundbreaking work opens new avenues for the development of high-performance, air-stable, and flexible n-type TE material, ushering in a new era for wearable TEGs.

Surface phosphorylated Li5FeO4 prelithiation additive synergistically improves the air-stability and lithium-ion conductivity

Because of the higher delithiation capacity, Li5FeO4 (LFO) can be used as sacrificial prelithiation additive to compensate the initial capacity loss caused by the formation of solid electrolyte interphase in lithium-ion batteries (LIBs). However, the extremely poor air stability and severe phase transition after Li+ deintercalation make it difficult for LFO to be applied in prelithiation engineering practice. Herein, the residual alkali layer generated on the LFO due to air exposure is directly converted into a Li3PO4 layer by a one-pot solid–liquid reaction. The as-obtained surface phosphorylated LFO (LP-LFO) ensures high air stability and effective prelithiation capability. Introducing only 3 wt% LP-LFO to the LiFePO4/Li half-cell can maximally replenish the active Li+ loss and the initial coulombic efficiency, displaying a 9.9 % increase in the initial charge capacity. Moreover, the Li3PO4 coating enables LP-LFO to be a fast ionic conductor, not only inhibiting the phase transition of LFO, but also improving the electronic and ionic conductivity of the electrode, which is confirmed by the complementary tests of galvanostatic intermittent titration technique and electrochemical impedance spectroscopy, as well as the structure and morphology characterization. As a result, the LiFePO4/Li half-cell with LP-LFO additive exhibits a higher rate capability (144 mAh g−1 at 2 C) and cycle stability (157 mAh g−1 after 100 cycles at 0.1 C). And a 17.4 % increase in the discharge capacity and a 12.7 % increase in energy density after 200 cycles for the 3 wt% LP-LFO-added LiFePO4||graphite full cell is also achieved. This work provides a facile and efficient conversion strategy for the air-instable electrode additives, and furtherly broadens their industrial application prospect in high energy density LIBs.

α-CsPbI3 Quantum Dots ReRAM with High Air Stability Working by Valance Change Filamentary Mechanism.

The current memory system is facing obstacles to improvement, and ReRAM is considered a powerful alternative. All-inorganic α-CsPbI3 perovskite-based ReRAM working by electrochemical mechanism is reported, but the electrochemically active electrode raised difficulty in long-term stable operation, and bulk α-CsPbI3 device can not show resistive switching behavior with an inert metal top electrode. Herein, by making the α-CsPbI3 into QDs and applying it to the device with inert Au as the top electrode, the devices working by valence change mechanism are successfully fabricated. The large surface-to-volume ratio made an abundant amount of iodine vacancies and facile migration of vacancies allowed the device to work by valence change mechanism. The devices show reliable electrical characteristics, 800 cycles endurance and retention for over 4 × 104 s, and air stability for 1 month. This work demonstrates that applying the QDs can improve the stability and enable a new type of working mechanism in ReRAM.

Triple-doped Argyrodite Sulfide Electrolyte with Improved Air Stability and Lithium Compatibility for All-Solid-State Li-Metal Batteries

The shift to electric vehicles has highlighted challenges associated with lithium-ion batteries, and the need for safer and higher-energy–density all-solid-state batteries. However, sulfide-based solid electrolytes face problems with moisture reactivity and poor Li metal compatibility. In this study, we synthesized a Li5.4Al0.1P1−xSbxS4.7−2.5xO2.5xCl1.3 electrolyte, employing a dual-doping strategy inspired by the “hard and soft acids and bases” theory to enhance ionic conductivity, air stability, and Li metal compatibility. Sb–O dopants were introduced into Cl–Al-doped argyrodite solid electrolytes, achieving an optimized electrolyte with controlled dopant concentration. The electrolyte exhibited high ionic conductivity, excellent air stability, and Li metal compatibility. The all-solid-state Li metal battery showed promising initial discharge capacity. The improved air stability of Sb–O-doped electrolytes is attributed to the formation of Sb–S and P–O bonds, which reduces H2S emission by 78 % upon moisture exposure, effectively suppressing reactions with moisture. Enhanced Li metal compatibility induces the formation of Li–Sb alloy at the anode interface, inhibiting the growth of Li-dendrites. The Li symmetric cell demonstrates high critical current density and outstanding cycling stability. This study offers a sulfide electrolyte design for all-solid-state Li metal batteries, showcasing its potential for practical application with high air stability and Li metal compatibility.

Engineering ternary hydrated eutectic electrolytes to realize rechargeable cathode-free aluminum-ion batteries

Aluminum-ion batteries (AIBs) have been highlighted as a promising candidate for large-scale energy storage due to the abundant reserve, low cost, high specific capacity, and good safety of aluminum. However, the development of AIBs is hindered by the usage of expensive, corrosive, and humidity-sensitive AlCl3-based ionic liquid electrolytes. Herein, we develop a low-cost, non-corrosive, and air-stable ternary hydrate eutectic electrolyte (HEE) composed of aluminum nitrate hydrate, manganese nitrate hydrate, and N,N-dimethylacetamide for cathode-free AIBs. The solvation structure of metal cations and water state in the electrolyte are regulated through the coordination of both water and N,N-dimethylacetamide molecules. The unique structural features of the HEE enables reversible deposition/stripping of AlxMnO2 on the cathodic current collector that are confirmed by various in-situ and ex-situ characterizations, ultimately realizing cathode-free AIBs. The architected cathode-free AIB delivers a discharge specific capacity of 361 mAh g−1 and shows good cycling stability and high air stability. This study provides a valuable insight into the design of rechargeable multi-valent metal ion batteries for advanced large-scale energy storage systems.

Synthesis of Li3+xP1-xGexS4-2xO2x electrolyte materials with high ionic conductivity and air stability by doping of GeO2 for all-solid-state lithium batteries

Synthesis of Li3+xP1-xGexS4-2xO2x electrolyte materials with high ionic conductivity and air stability by doping of GeO2 for all-solid-state lithium batteries

Designing the Interface Layer of Solid Electrolytes for All-Solid-State Lithium Batteries.

Li1.3Al0.3Ti1.7(PO4)3 (LATP) is one of the most attractive solid-state electrolytes (SSEs) for application in all-solid-state lithium batteries (ASSLBs) due to its advantages of high ionic conductivity, air stability and low cost. However, the poor interfacial contact and slow Li-ion migration have greatly limited its practical application. Herein, a composite ion-conducting layer is designed at the Li/LATP interface, which a MoS2 film is constructed on LATP via chemical vapor deposition, followed by the introduction of a solid polymer (SP) liquid precursor to form a MoS2@SP protective layer. This protective layer not only achieves a lower Li-ion migration energy barrier, but also adsorbs more Li-ion, which is able to promote interfacial ion transport and improve interfacial contacts. Thanks to the improved migration and adsorption of Li-ion, the Li symmetric cell containing LATP-MoS2@SP exhibits a stable cycle of more than 1200h at 0.1mAcm-2. More remarkably, the capacity retention of the full cell assembled with LiFePO4 cathode is as high as 86.2% after 400 cycles at 1C. This work provides a design strategy for significantly improving unstable interfaces of SSEs and realizing high-performance ASSLBs.

AgF-PEO composite interfacial layer for electrolyte-free LAGP-based lithium metal batteries

NASICON-type LAGP solid state electrolyte has become one of the most promising solid-state electrolytes due to its superior performance such as favorable room-temperature ionic conductivity, high stability in air, wide electrochemically stable window, and low cost. The key constraint to the development of LAGP electrolyte is the LAGP/Li interface problem. In this paper, a composite interfacial layer (AgF@Li-PEO@LAGP) is introduced between LAGP electrolyte and electrode material. The LiF and Ag nanoparticles are generated on the Li surface by utilizing the substitution reaction to uniform lithium flux and prevent the side reaction, while the flexible PEO polymer buffer layer on the LAGP will improve the interface wettability. The Li/LAGP/Li symmetric cell modified with composite interfacial layer can maintain a low polarization voltage of 0.11 V at 0.1 mA cm−2 for stable cycling for more than 1200 h. The full cell also shows excellent cycling stability with the capacity retention of 93.6 % after 100 cycles. The composite interface layer can realize the elimination of liquid electrolyte and greatly reduce interface resistance. This broadens the road for the realization of all-solid-state batteries.

Magnetic domain structures in ultrathin Bi2Te3/CrTe2 heterostructures

Abstract Chromium tellurium compounds are important two-dimensional van der Waals ferromagnetic materials with high Curie temperature and chemical stability in air, which is promising for applications in spintronic devices. Here, high-quality spin-orbital-torque (SOT) device, Bi2Te3/CrTe2 heterostructure was epitaxially grown on Al2O3 (0001) substrates. Anomalous Hall measurements indicate the existence of strong ferromagnetism in this device with the CrTe2 thickness down to 10 nm. In order to investigate its micromagnetic structure, cryogenic magnetic force microscope (MFM) was utilized to measure the magnetic domain evolutions at various temperatures and magnetic fields. The virgin domain state of the device shows a worm-like magnetic domain structure with the size around 0.6 ~ 0.8 µm. Larger irregular-shape magnetic domains (＞1µm) can be induced and pinned, after the field is increased to coercive field and ramped back to low fields. The temperature-dependent MFM signals exhibit a nice mean-field-like ferromagnetic transition with Curie temperature around 201.5 K, indicating a robust ferromagnetic ordering. Such device can be potentially implemented in future magnetic memory technology.

The deposition and the optical characteristics of Cu-based metal halide Cs3Cu2I5 thin film via mist deposition

Cu-based metal halides, such as Cs3Cu2I5, are promising materials for LEDs, photodetectors, and scintillators because of their excellent optical properties, nontoxicity, and high air stability. In this study, we demonstrated the deposition of high-coverage Cs3Cu2I5 thin films using solution-based mist deposition. By adjusting the substrate temperature appropriately, continuous Cs3Cu2I5 thin films were formed. The Cs3Cu2I5 thin films exhibited blue emission under ultraviolet irradiation, with a large Stokes shift of 1.40 eV. Furthermore, they exhibited a high photoluminescence quantum yield of over 80%.

Thinning Solution‐proceed 2D Te for p‐ and n‐channel Junction Field Effect Transistor with High Mobility and Ideal Subthreshold Slope

AbstractTwo‐dimensional non‐layered tellurene (Te) can serve as a promising candidate in transistor applications because of its high carrier mobility and air stability. However, it is still quite challenging in aspect of ultra‐thin channel and gate‐control ability in conventional metal‐oxide‐semiconductor field‐effect transistor architecture. This work proposes a facile thinning strategy for solution‐proceed Te flakes and fabricates a junction field‐effect transistor (JFET) architecture, that has well addressed the above‐mentioned two issues. Through a mild oxidative thinning process, the post‐growth Te flakes are thinned from bulk to few‐layer, guaranteeing the highly efficient electrostatic doping as a transistor channel. Then, a four‐terminal JFET‐based on p‐Te and n‐ReS2 is designed, achieving a multifunctional integration of rectification diode, p‐ and n‐channel transistor in one single device. By accessing different contact scheme, the ReS2/Te p‐n diode is explored with a rectification ratio of 103, the p‐channel JFET exhibits a high hole mobility of 317.6 cm2V−1s−1, ideal low subthreshold swing of 84 mV dec−1. While the n‐channel JFET is obtained with electron mobility of 67.6 cm2 V−1s−1 and SS of 229 mV dec−1. Both p‐ and n‐channel devices showcase clear saturation characteristic with ultra‐small pinch‐off voltage (≈0.4 V), which is crucial for low‐power logical and integrated circuit applications.

Nucleophilic Aromatic Substitution (SNAr) as an Approach to Challenging Nitrogen-Bridged BODIPY Oligomers.

A series of nitrogen-bridged BODIPY oligomers were synthesized via nucleophilic aromatic substitution (SNAr) as a convenient approach. Further transformations achieved novel α,α-aryl BODIPY dimers as well as a BODIPY hexamer efficiently. These BODIPY oligomers showed good photophysical properties, such as apparent absorption and emission both in visible and near-infrared regions. Interestingly, the high air and photothermal stability, strong NIR absorption, and high photothermal conversion rates of hexamer B6 suggest potential applications in photothermal therapy.

Preparation and electrochemical properties of a ceramic solid electrolyte with high ionic conductivity, Li1.3Al0.3Ti1.7(PO4)3

The emergence of lithium-ion solid electrolytes greatly increases the safety risk of liquid electrolytes. Among the many solid electrolytes, aluminum-doped Li1.3Al0.3Ti1.7(PO4)3(LATP) has become a research hotspot due to its high ionic conductivity and good air stability. However, the traditional high-temperature sintering process has the problems of lithium volatilization and secondary phase formation. Therefore, it is very difficult to prepare high-quality LATP solid electrolytes. The X-ray diffraction pattern and analysis showed that the LATP samples prepared in this paper showed rhombohedral structure and could be indexed by the R3c space group, and a new method of excess lithium compensation sintering was proposed, in which lithium compensation (LiNO3) could well reduce the impact of lithium volatilization. It can be used as a sintering additive to promote the sintering densification of LATP. In this paper, the optimal sample for sintering at 900°C was determined by measuring the microstructure and electrochemical properties of the electrolyte, and lithium doping was studied. The LATP solid electrolyte with 10 wt% lithium doped has a conductivity of 7.2× 10−4 S/cm and a low activation energy (0.278 eV). Its mechanical properties (elastic modulus and hardness) are the best, which are 103.024 GPa and 8.053 GPa, respectively, and the value of its elastic modulus is much greater than that of lithium metal shear modulus of 4.25 GPa, which can effectively inhibit the growth of lithium dendrites. And the magnitude of the grain boundary conductivity and particle size of the lithium-doped sample correspond to the dielectric constant results.

Anion-doped Na2.9Fe1.7(SO4)2.7(PO4)0.3 cathode with improved cyclability and air stability for low-cost sodium-ion batteries

Polyanion-type Fe-based sulfates are one of the most promising cathode candidates for sodium-ion batteries (SIBs) due to the low cost and high voltage. However, their practical application is still hindered by the poor air stability. Herein, we report a novel anion-doped Na2.9Fe1.7(SO4)2.7(PO4)0.3 cathode material with higher air stability and faster ion/electron transport kinetics compared to pristine Na2.6Fe1.7(SO4)3 cathode as evidenced by first-principles calculations. The obtained Na2.9Fe1.7(SO4)2.7(PO4)0.3 not only manifests a high discharge capacity of 100.4 mAh g−1 with an operating voltage of ∼3.57 V (Na+/Na), but also exhibits excellent rate performance (∼86.7 mAh g−1 at 30 C) and cycle stability over 6000 cycles (capacity retention of 76.3%). Particularly, Na2.9Fe1.7(SO4)2.7(PO4)0.3 cathode still maintain its original crystal structural and sodium-storage property after exposure to air for one week. The high-voltage, long-life, and air-stable Na2.9Fe1.7(SO4)2.7(PO4)0.3 could be a competitive cathode candidate for low-cost sodium-ion batteries.

CAN Interceded Oxidative Coupling of β‐Dicarbonyl Compounds to 2‐Aryl/Heteroarylchromenes: A Regio‐ and Diastereoselective Synthesis of Tetrahydro‐benzofuro[3,2‐c]chromenones

AbstractA promising and useful method has been accomplished for regio‐ and diastereoselective synthesis of tetrahydro‐benzofuro[3,2‐c]chromenones through ceric(IV) ammonium nitrate (CAN) mediated oxidative coupling of cyclic/acyclic 1,3‐dicarbonyl compounds to 2‐aryl/heteroarylchromenes followed by a base assisted cyclization. The significant features of the method encircle easy accessibility of the starting materials, high air stability and low toxicity of oxidant CAN, high product yield, operationally simple and eco‐friendly reaction conditions. Trapping of a radical intermediate with radical scavenger TEMPO (detected by LC–MS) from the reaction mixture proved that the oxidative coupling is a radical mediated process.

Synthesis of ultra-small Co3O4-C core-shell nanoparticles with improved thermal stability and microwave absorption properties

Ultra-small Co3O4-C nanoparticles were synthesized with an average core size of 8.2 nm by annealing CoC nanoparticles in air at a relative low temperature. The formation mechanism of these nanoparticles can be attributed to the presence of defective C shells, the high chemical activity of ultra-small Co nanoparticles, and the gradual oxidation of the C shell during the low-temperature annealing process. The Co3O4-C nanoparticles demonstrated remarkable thermal stability at temperatures of up to 360 °C in air. Moreover, he Co3O4-C nanoparticles exhibited excellent microwave absorption performances, with an optimal reflection loss of −64.2 dB and an effective bandwidth of 6.08 GHz at a single thickness of 2.2 mm. These impressive microwave absorption properties can be attributed to the small size effects, the core-shell nanostructure, and the presence of defective C shells in the nanoparticles. Overall, the as-synthesized Co3O4-C nanoparticles show great potential for future applications as microwave absorbers, thanks to their large bandwidth, strong microwave absorption, and high thermal stability in air.

Magnetoresistance properties in nickel-catalyzed, air-stable, uniform, and transfer-free graphene

A transfer-free graphene with high magnetoresistance (MR) and air stability has been synthesized using nickel-catalyzed atmospheric pressure chemical vapor deposition. The Raman spectrum and Raman mapping reveal the monolayer structure of the transfer-free graphene, which has low defect density, high uniformity, and high coverage (>90%). The temperature-dependent (from 5 to 300 K) current–voltage (I–V) and resistance measurements are performed, showing the semiconductor properties of the transfer-free graphene. Moreover, the MR of the transfer-free graphene has been measured over a wide temperature range (5–300 K) under a magnetic field of 0 to 1 T. As a result of the Lorentz force dominating above 30 K, the transfer-free graphene exhibits positive MR values, reaching ∼8.7% at 300 K under a magnetic field (1 Tesla). On the other hand, MR values are negative below 30 K due to the predominance of the weak localization effect. Furthermore, the temperature-dependent MR values of transfer-free graphene are almost identical with and without a vacuum annealing process, indicating that there are low density of defects and impurities after graphene fabrication processes so as to apply in air-stable sensor applications. This study opens avenues to develop 2D nanomaterial-based sensors for commercial applications in future devices.

Controlling Sodium Dendrite Growth via Grain Boundaries in Na3Zr2Si2PO12 Electrolyte

AbstractNa3Zr2Si2PO12(NZSP)‐based NASICON solid‐state electrolytes (SSEs) show not only competitive ionic conductivity but also high chemical stability in air, holding a great promise for enabling the use of sodium metal anode in solid‐state sodium batteries. However, sodium (Na) metal dendrite growth inside SSE always leads to undesirable short‐circuiting in battery even no obvious changes in interfacial contact loss and interfacial decomposition during cycling. How to control Na metal dendrite growth and in situ observe the effect of SSE/Na interface change on dendrite growth is quite challenging. Herein, an in situ synchrotron‐based X‐ray imaging method is developed to systematically investigate the dendrite origin in NZSP‐based SSEs. It is find that the dendrite growth intrinsically depends on the grain boundaries (GBs) in NZSP and the NZSP/Na interfacial properties. It is confirmed that Na dendrite infiltration kinetic evolution in NZSP is strongly associated with Na ion/electron conductivity and Young's modulus of GBs. Moreover, the electro‐chemo‐mechanical phase‐field model evaluation demonstrates that the basic reason for Na metal dendrite intrusion into the GBs of SSE is a combination of local polarization potential and the presence of stress formed at GBs.

Stable photothermal conversion in single-walled carbon nanotube device with pn-junction under uniform sunlight irradiation

N-type single-walled carbon nanotube (SWCNT) films with high air stabilities have attracted significant attention for their potential application in SWCNT devices featuring pn-junctions for power generation. However, SWCNT devices must be locally heated or formed into suspended structures to generate a temperature difference and produce output power. In this study, pn-junction SWCNT films were fabricated via vacuum filtration and subsequently attached to a polyimide substrate, enabling the creation of SWCNT devices without the need for suspended structures. Upon uniform irradiation with artificial sunlight, the SWCNT device produced a stable output voltage and short-circuit photocurrent. A thermographic image showed the emergence of a temperature gradient originating from the center of the SWCNT film and extending to the edge of the polyimide substrate. This phenomenon can be attributed to the higher optical absorption of SWCNT films compared to that of polyimide substrates. Consequently, the diffusion of carriers within the device generated an electric potential difference. Therefore, the SWCNT device generated a temperature gradient and yielded output power under uniform sunlight irradiation. These findings may aid in the development of facile and flexible optical devices, including photodetectors and hybrid devices integrating solar cells.