Revealing the Subzero-Temperature Electrochemical Kinetics Behaviors in Ni-Rich Cathode.

The sluggish kinetics in Ni-rich cathodes at subzero temperatures causes decreased specific capacity and poor rate capability, resulting in slow and unstable charge storage. So far, the driving force of this phenomenon remains a mystery. Herein, with the help of in-situ X-ray diffraction and time of flight secondary ion mass spectrometry techniques, the continuous accumulation of both the cathode electrolyte interphase (CEI) film formation and the incomplete structure evolution during cycling under subzero temperature are proposed. It is presented that excessively uniform and thick CEI film generated at subzero temperatures would block the diffusion of Li+ -ions, resulting in incomplete phase evolution and clear charge potential delay. The incomplete phase evolution throughout the Li+ -ion intercalation/de-intercalation processes would further cause low depth of discharge and poor electrochemical reversibility with low initial Coulombic efficiency, as well. In addition, the formation of the thick and uniform CEI film would also consume Li+ -ions during the charging process. This discovery highlights the effects of the CEI film formation behavior and incomplete phase evolution in restricting electrochemical kinetics under subzero temperatures, which the authors believe would promote the further application of the Ni-rich cathodes.

Highly Stable Mo-NiO@NiFe-Layered Double Hydroxide Heterojunction Anode Catalyst for Alkaline Electrolyzers with Porous Membrane.

Heterostructure catalysts are considered as promising candidates for promoting the oxygen evolution reaction (OER) process due to their strong electron coupling. However, the inevitable dissolution and detachment of the heterostructure catalysts are caused by the severe reconstruction, dramatically limiting their industrial application. Herein, the NiFe-layered double hydroxide (LDH) nanosheets attached on Mo-NiO microrods (Mo-NiO@NiFe LDH) by the preoxidation strategy of the core NiMoN layer are synthesized for ensuring the high catalytic performance and stability. Owing to the enhanced electron coupling and preoxidation process, the obtained Mo-NiO@NiFe LDH exhibits a superlow overpotential of 253 mV to achieve a practically relevant current density of 1000 mA cm-2 for OER with exceptional stability over 1200 h. Notably, the overall water splitting system based on Mo-NiO@NiFe LDH reveals remarkable stability, maintaining the catalytic activity at a current density of 1000 mA cm-2 for 140 h under industrial harsh conditions. Furthermore, the Mo-NiO@NiFe LDH demonstrates outstanding activity and long-term durability in a practical alkaline electrolyzer assembly with a porous membrane, even surpassing the performance of IrO2. This work provides a new sight for designing and synthesizing highly stable heterojunction electrocatalysts, further promoting and realizing the industrial electrocatalytic OER.

In Situ Construction of Biphasic Boride Electrocatalysts on Dealloyed Bulk Ni-Mo Alloy as Self-Supporting Electrode for Water Splitting at High Current Density.

Nickel-molybdenum-boron (Ni-Mo-B)-based catalysts with biphasic interfaces are highly advantageous in bifunctional electrocatalytic activity in alkaline water-splitting. However, it remains an ongoing challenge to obtain porous Ni-Mo alloy substrates that provide stable adhesion to catalysts, ensuring the long-term performance of bifunctional self-supporting electrodes at a high current density. Herein, a porous Ni-Mo alloy substrate was effectively obtained by a cost-effective dealloying process on a commercial Ni-Mo alloy with high-energy crystal planes. Subsequently, the Mo2NiB2/Ni3B bifunctional catalyst was in situ synthesized on this substrate via boriding heat treatment, resulting in outstanding catalytic activity and stability. Density functional theory (DFT) calculations reveal that the abundant biphasic interfaces and surface-reconstructed sites of the Mo2NiB2/Ni3B catalyst can decrease the energy barriers for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Thus, the designed self-supporting electrodes show bifunctional catalytic activity with overpotentials of 151 mV for HER and 260 mV for OER at a current density of 10 mA cm-2. Markedly, the assembled water electrolyzer can be driven up to 10 mA cm-2 at 1.64 V and maintain catalytic activity at a high current density of 1000 mA cm-2 for 100 h. The new strategy is expected to provide a low-cost scheme for designing self-supporting bifunctional electrodes with high activity and excellent stability and contribute to the development of hydrogen energy technology.

Hexagonal MoO3 Anode with Extremely High Capacity and Cyclability for Lithium-Ion Battery: A Combined Theoretical and Experimental Study.

It is essential and still remains a big challenge to obtain fast-charge anodes with large capacities and long lifespans for Li-ion batteries (LIBs). Among all of the alternative materials, molybdenum trioxide shows the advantages of large theoretical specific capacity, distinct tunnel framework, and low cost. However, there are also some key shortcomings, such as fast capacity decaying due to structural instability during Li insertion and poor rate performance due to low intrinsic electron conductivity and ion diffusion capability, dying to be overcome. A unique strategy is proposed to prepare Ti-h-MoO3-x@TiO2 nanosheets by a one-step hydrothermal approach with NiTi alloy as a control reagent. The density functional theory (DFT) calculations indicate that the doping of Ti element can make the hexagonal h-MoO3-x material show the best electronic structure and it is favor to be synthesized. Furthermore, the hexagonal Ti-h-MoO3-x material has better lithium storage capacity and lithium diffusion capacity than the orthogonal α-MoO3 material, and its theoretical capacity is more than 50% higher than that of the orthogonal α-MoO3 material. Additionally, it is found that Ti-h-MoO3-x@TiO2 as an anode displays extremely high reversible discharge/charge capacities of 1326.8/1321.3 mAh g-1 at 1 A g-1 for 800 cycles and 611.2/606.6 mAh g-1 at 5 A g-1 for 2000 cycles. Thus, Ti-h-MoO3-x@TiO2 can be considered a high-power-density and high-energy-density anode material with excellent stability for LIBs.