Revealing the Impact of Dual Site Modification on the Phase Transformation and Ion Transport Mechanism of Ni-Rich Cathode Materials.

Ni-rich cathode materials have garnered significant attention attributable to the high reversible capacity and superior rate performance, particularly in the electric vehicle industry. However, the structural degradation experienced during cycling results in rapid capacity decay and deterioration of the rate performance, thereby impeding the widespread application of Ni-rich cathodes. Herein, a Mg/Ti co-doping strategy was developed to boost the structure stability and Li-ion transport kinetics of the Ni-rich cathode material LiNi0.90Co0.05Mn0.05O2 (NCM9055) under long cycle. It is demonstrated that the Mg2+ ions inserted into the lithium layer could serve as pillars, enhancing the stability of the delithiated layer structure. The introduction of robust Ti-O bonding mitigated the detrimental H2-H3 phase transition (∼4.2 V) during cycling. In addition, despite the fact that Mg/Ti co-doping slightly reduces Li+ diffusion coefficient in the modified cathode material (NCM9055-MT), it effectively stabilized the robustness of the layered structure and maintained the Li+ diffusion channel while charging and discharging, thereby improving the Li+ diffusion coefficient after a long cycle. Therefore, the Mg/Ti co-doped cathode materials exhibited an exceptional capacity retention rate of 99.9% (100 cycles, 1 C). Additionally, the Li+ diffusion coefficient of the co-doped NCM9055-MT (2.924 × 10-10 cm2 s-1) after 100 cycles was effectively enhanced compared with the case of undoped NCM9055 (4.806 × 10-11 cm2 s-1). This work demonstrates that the Mg/Ti co-doping approach effectively enhanced the stability of layered Ni-rich cathode materials.

The in situ phosphorization inducing oxygen vacancies in the core-shell structured NiFe oxides boosts the electrocatalytic activity for the oxygen evolution reaction.

Transition metal-based oxides have been reported as an important family of electrocatalysts for water splitting owing to their possible large-scale applications that are highly desirable for the hydrogen generation industry. Herein, we report a facile method for the preparation of phosphate-decorated NiFe oxides on nickel foam as efficient oxygen evolution reaction (OER) electrocatalysts for water oxidation. The OER electrocatalysts were developed through the pyrolysis of MIL(Fe) metal-organic frameworks (MOFs), which were modified with Ni and P species. It was found that the formation of NiO on the Fe2O3 surface (NiO@Fe2O3) can enrich electrocatalytic active sites for the OER. Meanwhile, the incorporation of P into NiO@Fe2O3 (Px-NiO@Fe2O3) creates abundant oxygen vacancies, which facilitates the surface charge transfer for OER electrocatalysis. Benefiting from the structure and composition advantages, P2.0-NiO@Fe2O3/NF exhibits the best performance for OER electrocatalysis among other prepared electrocatalysts, with an overpotential of 208 mV at the OER current density of 10 mA cm-2 and a small Tafel slope of 69.64 mV dec-1 in 1 M KOH solution. Additionally, P2.0-NiO@Fe2O3/NF shows an outstanding durability for the OER electrocatalysis, maintaining the OER current density above 20 mA cm-2 for more than 100 h.

Electrochemical incorporation of heteroatom into surface reconstruction induced Ni vacancy of NixO nanosheet for enhanced water oxidation.

Surface reconstruction of non-oxide oxygen evolution reaction (OER) electrocatalysts has been intensively studied to improve their catalytic performances. However, further modification of the reconstructed active surfaces for better catalytic performances has not been reported. In this work, NiSe nanorods are prepared on nickel foam (NiSe@NF) as the pre-catalyst for electrochemical OER. It is revealed that non-stoichiometric NiO nanosheets with abundant Ni vacancies (NixO) are formed on the surfaces of NiSe nanorods (NixO/NiSe@NF) via in-situ electrochemical oxidation. Furthermore, the OER performances are obviously improved after heteroatom Fe is incorporated electrochemically into NixO nanosheets ((FeNi)O/NiSe@NF). For OER to have a current density of 20 mA cm-2 in 1 M KOH solution, the as-prepared (FeNi)O/NiSe@NF electrode only needs an overpotential of 268 mV. Density functional theory (DFT) calculations reveal that the formation of Ni vacancy can increase the free energy of *OH. More importantly, the incorporation of heteroatom Fe into Ni vacancy can significantly decrease the free energy of *O, which enables Fe-NiO to have the lowest theoretical overpotential for OER in this work. The present work provides a facile and universal strategy to modify the reconstructed active oxides' surfaces for higher electrocatalytic performances.

In-situ reconstruction of non-noble multi-metal core-shell oxyfluorides for water oxidation.

The electrochemical anodic behavior of transition metal compounds plays an undeniably non-negligible role across many electrooxidation reactions. In this work, a chronopotentiometric technique was employed to activate the multicomponent non-noble metal oxyfluorides in-situ for oxygen evolution reaction (OER). It is interesting to unravel that the increasing applied current density helps to reconstruct the catalyst into nanoporous core-shell structure and introduce metal oxyhydroxide on the surface, which guarantees more channels for efficient ion/mass transportation and thus contributes to exposing more active sites for catalytic reaction. The activated five-membered oxyfluoride shows the best catalytic activity with overpotential of 348 ± 2 mV to achieve the current density of 10 mA/cm2 and a Tafel slope of 110.3 ± 0.1 mV/dec, in contrast with the pristine one (532 ± 2 mV & 240.2 ± 0.1 mV/dec). It still maintains high stability after long time OER measurement, making it a promising succedaneum for noble metal catalysts. The high-entropy effect, amorphous state and high active sites density jointly contribute to its enhanced OER performance. This work provides new ideas for realizing the potential of inactive elements via entropy engineering and using electrochemical self-reconstruction to modify semiconductors for advanced water oxidation.

Stabilizing Oxygen Vacancy in Entropy-Engineered CoFe2O4-Type Catalysts for Co-prosperity of Efficiency and Stability in an Oxygen Evolution Reaction.

We used entropy engineering to design a series of CoFe2O4-type spinels. Through microstructural characterization, electrochemical measurements, and X-ray photoelectron spectroscopy, we demonstrated that the entropy-stabilized oxide (Co0.2Mn0.2Ni0.2Fe0.2Zn0.2)Fe2O4 has a single-phase spinel structure and exhibits both efficient and stable catalytic oxygen evolution. This is attributable to disordered occupation of multivalent cations, which induces severe lattice distortion and increases configurational entropy, thereby facilitating formation of structurally stable, high-density oxygen vacancies on the exposed surface of the spinel. Thus, more catalytic sites on the surface are activated and retained over the course of long-duration testing for oxygen evolution. Entropy engineering expands researchers' access to catalysts that link entropy-stabilized structures to useful properties.

Rapid decoloration of azo dye Direct Blue 6 by AlCrFeMn high entropy alloy.

In recent years, high entropy alloys (HEAs) have attracted a lot of attention from researchers due to their outstanding mechanical properties, but there are few reports about their functional performance. The development of new functional applications of HEAs is a challenging, but very meaningful topic. The decoloration of azo dye Direct Blue 6 (DB6) using equiatomic AlCrFeMn HEA synthesized by ball-milling is reported in this study. Ball-milled (BM) AlCrFeMn HEA shows excellent performance in the decoloration of DB6, 3 times faster than BM MgZn-based glassy powders and AlCoCrTiZn HEA, which are reported as the best among the metallic glasses and HEAs so far, respectively. The effects of initial pH, initial temperature and dye concentrations on the decoloration efficiency during reaction are systematically studied. This work can greatly expand the applications of HEAs, especially the application of their functional properties.