Layered Na2Ti3O7 as an Ultrastable Intercalation-Type Anode for Non-Aqueous Calcium-Ion Batteries.

Calcium ion batteries (CIBs) are a promising energy storage device due to the low redox potential of the Ca metal and the abundant reserves of the Ca element. However, the large radius and divalent nature of Ca2+ lead to its slow ion diffusion kinetics and the lack of suitable electrode materials for Ca storage. Here, a layered structure of Na2Ti3O7 (NTO) is presented as an anode material for nonaqueous CIBs. This NTO anode demonstrates a high discharge capacity of 165 mA h g-1 at 100 mA g-1 and a remarkable capacity retention rate of 80%, even after 2000 cycles at 500 mA g-1, surpassing the performance of all reported intercalation-type anode materials for CIBs. The NTO transfers to layered CaVIINaIXTi3O7 (CNTO) with intercalation of Ca2+ and extraction of Na+ during the first discharge process. Then, the CNTO undergoes the reversible insertion/extraction of Ca2+ during subsequent cycling. Additionally, density functional theory calculations reveal that NTO possesses a rapid two-dimensional diffusion pathway for Ca2+. Moreover, the full CIBs based on NTO as the anode further underscore its potential for CIBs. This work presents promising anode materials for CIBs, offering opportunities to promote the development of high-performance CIBs.

Trigger a multi-electron reaction by tailoring electronic structure of VO2 toward more efficient aqueous zinc metal batteries.

VO2 (B) is recognized as a promising cathode material for aqueous zinc metal batteries (AZMBs) owing to its remarkable specific capacity and its unique, expansive tunnel structure, which facilitates the reversible insertion and extraction of Zn2+. Nonetheless, challenges such as the inherent instability of the VO2 structure, poor ion/electron transport and a limited capacity due to the low redox potential of the V3+/V4+ couple have hindered its wider application. In this study, we present a strategy to replace vanadium ions by doping Al3+ in VO2. This approach activates the multi-electron reaction (V4+/V5+), to increase the specific capacity and improve the structural stability by forming robust V5+O and Al3+O bonds. It also induces a local electric field by altering the local electron arrangement, which significantly accelerates the ion/electron transport process. As a result, Al-doped VO2 exhibits superior specific capacity, improved cycling stability, and accelerated electronic transport kinetics compared to undoped VO2. The beneficial effects of heterogeneous atomic doping observed here may provide valuable insights into the improvement electrode materials in metal-ion battery systems other than those based on Zn.

"Triple-synergistic effect" of K+ and PANI co-intercalation enabling the high-rate capability and stability of V2O5 for aqueous zinc-ion batteries.

Vanadium-based materials are widely recognized as the primary candidate cathode materials for aqueous Zn-ion batteries (AZIBs). However, slow kinetics and poor stability pose significant challenges for widespread application. Herein, to address these issues, alkali metal ions and polyaniline (PANI) are introduced into layered hydrated V2O5 (VO). Density functional theory calculations reveal that the synthesized (C6H4NH)0.27K0.24V2O5·0.92H2O (KPVO), with K+ and PANI co-intercalation, exhibits a robust interlayer structure and a continuous three-dimensional (3D) electron transfer network. These properties facilitate the reversible diffusion of Zn2+ with a low migration potential barrier and rapid response kinetics. The KPVO cathode exhibits a discharge specific capacity of 418.3 mAh/g at 100 mA/g and excellent cycling stability with 89.5 % retention after 3000 cycles at 5 A/g. This work provides a general strategy for integrating cathode materials to achieve high specific capacity and excellent kinetic performance.