Recent Advances in Understanding of the Singlet Oxygen in Energy Storage and Conversion.

Singlet oxygen (term symbol 1 Δg , hereafter 1 O2 ), a reactive oxygen species, has recently attracted increasing interest in the field of rechargeable batteries and electrocatalysis and photocatalysis. These sustainable energy conversion and storage technologies are of vital significance to replace fossil fuels and promote carbon neutrality and finally tackle the energy crisis and climate change. Herein, the recent progresses of 1 O2 for energy storage and conversion is summarized, including physical and chemical properties, formation mechanisms, detection technologies, side reactions in rechargeable batteries and corresponding inhibition strategies, and applications in electrocatalysis and photocatalysis. The formation mechanisms and inhibition strategies of 1 O2 in particular aprotic lithium-oxygen (Li-O2 ) batteries are highlighted, and the applications of 1 O2 in photocatalysis and electrocatalysis is also emphasized. Moreover, the confronting challenges and promising directions of 1 O2 in energy conversion and storage systems are discussed.

Experimentally validated design principles of heteroatom-doped-graphene-supported calcium single-atom materials for non-dissociative chemisorption solid-state hydrogen storage.

Non-dissociative chemisorption solid-state storage of hydrogen molecules in host materials is promising to achieve both high hydrogen capacity and uptake rate, but there is the lack of non-dissociative hydrogen storage theories that can guide the rational design of the materials. Herein, we establish generalized design principle to design such materials via the first-principles calculations, theoretical analysis and focused experimental verifications of a series of heteroatom-doped-graphene-supported Ca single-atom carbon nanomaterials as efficient non-dissociative solid-state hydrogen storage materials. An intrinsic descriptor has been proposed to correlate the inherent properties of dopants with the hydrogen storage capability of the carbon-based host materials. The generalized design principle and the intrinsic descriptor have the predictive ability to screen out the best dual-doped-graphene-supported Ca single-atom hydrogen storage materials. The dual-doped materials have much higher hydrogen storage capability than the sole-doped ones, and exceed the current best carbon-based hydrogen storage materials.

New Insights into the Effects of Zr Substitution and Carbon Additive on Li3-xEr1-xZrxCl6 Halide Solid Electrolytes.

Halide solid electrolytes have been considered as the most promising candidates for practical high-voltage all-solid-state lithium-ion batteries (ASSLIBs) due to their moderate ionic conductivity and good interfacial compatibility with oxide cathode materials. Aliovalent ion doping is an effective strategy to increase the ionic conductivity of halide electrolytes. However, the effects of ion doping on the electrochemical stability window of halide electrolytes and carbon additive on electrochemical performance are still unclear by far. Herein, a series of Zr-doped Li3-xEr1-xZrxCl6 halide solid electrolytes (SEs) are synthesized through a mechanochemical method and the effects of Zr substitution on the ionic conductivity and electrochemical stability window are systematically investigated. Zr doping can increase the ionic conductivity, whereas it narrows the electrochemical stability window of the Li3ErCl6 electrolyte simultaneously. The optimized Li2.6Er0.6Zr0.4Cl6 electrolyte exhibits both a high ionic conductivity of 1.13 mS cm-1 and a high oxidation voltage of 4.21 V. Furthermore, carbon additives are demonstrated to be beneficial for achieving high discharge capacity and better cycling stability and rate performance for halide-based ASSLIBs, which are completely different from the case of sulfide electrolytes. ASSLIBs with uncoated LiCoO2 cathode and carbon additives exhibit a high discharge capacity of 147.5 mAh g-1 and superior cycling stability with a capacity retention of 77% after 500 cycles. This work provides an in-depth understanding of the influence of ion doping and carbon additives on halide solid electrolytes and feasible strategies to realize high-energy-density ASSLIBs.

A Redox Couple Strategy Enables Long-Cycling Li- and Mn-Rich Layered Oxide Cathodes by Suppressing Oxygen Release.

Li- and Mn-rich layered oxides (LMROs) are considered the most promising cathode candidates for next-generation high-energy lithium-ion batteries. The poor cycling stability and fast voltage fading resulting from oxygen release during charging, however, severely hinders their practical application. Herein, a strategy of introducing an additional redox couple is proposed to eliminate the persistent problem of oxygen release. As a proof of concept, the cycling stability of Li1.2 Ni0.13 Co0.13 Mn0.54 O2 , which is a typical LMRO cathode, is substantially enhanced with the help of the S2- /SO3 2- redox couple, and the capacity shows no decay with a retention of 100% after 700 cycles at 1C, far superior to the bare counterpart (61.7%). The surface peroxide ions (O2 2- ) are readily chemically reduced back to immobile O2- by S2- during charging, accompanied by the formation of SO3 2- , which plays a critical role in stabilizing the oxygen lattice and eventually inhibiting the release of oxygen. More importantly, the S2- ions are regenerated during the following discharging process and participate in the chemical redox reaction again. The findings shed light on a potential direction to tackle the poor cycling stability of high-energy anion-redox cathode materials for rechargeable metal-ion batteries.

A Novel Tin-Bonded Silicon Anode for Lithium-Ion Batteries.

Poor cyclic stability and low rate performance due to dramatic volume change and low intrinsic electronic conductivity are the two key issues needing to be urgently solved in silicon (Si)-based anodes for lithium-ion batteries. Herein, a novel tin (Sn)-bonded Si anode is proposed for the first time. Sn, which has a high electronic conductivity, is used to bond the Si-anode material and copper (Cu) current collector together using a hot-pressed method with a temperature slightly above the melting point of Sn. The cycling performance of the electrode is studied using a galvanostatic method. Nanoindentation and peeling tests are conducted to measure the mechanical strength of the electrodes. Direct current polarization and galvanostatic intermittent titration techniques are applied to assess the conductivity of the composites. Electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy are conducted to evaluate the effect of the coating layer on the cycling ability of the composites. The Sn-bonded Si anodes show superior cycling stability and high rate performance with an improved initial Coulombic efficiency. Analyses reveal that the low-melting-point Sn helps to markedly improve the electronic conductivity of the electrodes and serves as a metallic binder as well to enhance the adhesive strength of the electrode. It is hopeful that this novel Sn-bonded Si anode provides a new insight for the development of advanced Si-based anodes for LIBs.

Enhancement of Thermal and Mechanical Properties of Bismaleimide Using a Graphene Oxide Modified by Epoxy Silane.

A thermosetting resin system, based on bismaleimide (BMI), has been developed via copolymerization of 4,4'-diaminodiphenylsulfone with a newly synthesized graphene oxide modified using epoxy silane (ES-GO). The effect of ES-GO on the thermomechanical and mechanical properties of cured modified resin was studied. To evaluate the efficiency of the modified BMI systems, the composite samples using glass fiber cloth were molded and tested. Thermogravimetric analysis indicates that the cured sample systems displays a high char yield at lower concentrations of ES-GO (≤0.5 wt.%), suggesting an improved thermal stability. Using dynamic mechanical analysis, a marked increase in glass transition temperature (Tg) with increasing ES-GO content was observed. Analysis of mechanical properties reveals a possible effect of ES-GO as a toughener. The results also showed that the addition of 0.3 wt.% ES-GO maximizes the toughness of the modified resin systems, which was further confirmed by the result of analysis of fracture surfaces. At the same time, a molded composite with ES-GO showed improved mechanical properties and retention rate at 150 °C as compared to that made with neat resin.

Improved thermal and mechanical properties of bismaleimide nanocomposites via incorporation of a new allylated siloxane graphene oxide.

A thermosetting resin system based on bismaleimide (BMI) has been developed via copolymerization with 4,4'-diaminodiphenylsulfone in the presence of a newly synthesized graphene oxide, modified using allylated siloxane (AS-GO). The curing behavior of the AS-GO-containing resin system was evaluated using curing kinetics. The dispersibility of AS-GO in the resin was observed through polarizing optical microscopy (POM), which indicates that AS-GO has good dispersibility in the resin due to GO modified with allylated siloxane which has a good phase compatibility with BMI. The effect of AS-GO on the thermomechanical and mechanical properties of the cured modified resin was also studied. Results of thermogravimetric analysis indicated that the cured sample systems display a high char yield at lower concentrations of AS-GO (≤0.5 wt%) with an improved thermal stability. Using dynamic mechanical analysis, a marked increase in glass transition temperature (T g) with increasing AS-GO content was observed. Mechanical property analyses revealed a possible effect of AS-GO as a toughener, and the results showed that an addition of 0.3% AS-GO maximized the toughness of the modified resin systems, which was confirmed by analysis of fracture surfaces.

Over 20% Efficiency in Methylammonium Lead Iodide Perovskite Solar Cells with Enhanced Stability via "in Situ Solidification" of the TiO2 Compact Layer.

In methylammonium lead iodide (MAPbI3) perovskite solar cells (PSCs), the device performance is strongly influenced by the TiO2 electron transport layer (ETL). Typically, the ETL needs to simultaneously be thin and pinhole-free to have high transmittance and avoid shunting. In this work, we develop an "in situ solidification" process following spin coating in which the titanium-based precursor (titanium(diisopropoxide) bis(2,4-pentanedionate)) is dried under vacuum to rapidly achieve continuous TiO2 layers. We refer to this as "gas-phase quenching". This results in thin (60 ± 10 nm), uniform, and pinhole-free TiO2 films. The PSCs based on the gas-phase quenched TiO2 exhibits improved power conversion efficiency, with a median value of 18.23% (champion value of 20.43%), compared to 9.03 and 14.09% for the untreated devices. Gas-phase quenching is further shown to be effective in enabling efficient charge transfer at the MAPbI3/TiO2 heterointerface. Furthermore, the stability of the gas-phase quenched devices is enhanced in ambient air as well as under 1 sun illumination. In addition, we achieve 12.1% efficiency in upscaled devices (1.1 cm2 active area).