Quantitative Regulation of Interlayer Space of NH₄V₄O₁₀ for Fast and Durable Zn²⁺ and NH₄⁺ Storage

Abstract

Layered vanadium‐based oxides are the promising cathode materials for aqueous zinc‐ion batteries (AZIBs). Herein, an in situ electrochemical strategy that can effectively regulate the interlayer distance of layered NH4V4O10 quantitatively is proposed and a close relationship between the optimal performances with interlayer space is revealed. Specifically, via increasing the cutoff voltage from 1.4, 1.6 to 1.8 V, the interlayer space of NH4V4O10 can be well‐controlled and enlarged to 10.21, 11.86, and 12.08 Å, respectively, much larger than the pristine one (9.5 Å). Among them, the cathode being charging to 1.6 V (NH4V4O10‐C1.6), demonstrates the best Zn2+ storage performances including high capacity of 223 mA h g−1 at 10 A g−1 and long‐term stability with capacity retention of 97.5% over 1000 cycles. Such superior performances can be attributed to a good balance among active redox sites, charge transfer kinetics, and crystal structure stability, enabled by careful control of the interlayer space. Moreover, NH4V4O10‐C1.6 delivers NH4+ storage performances whose capacity reaches 296 mA h g−1 at 0.1 A g−1 and lifespan lasts over 3000 cycles at 5 A g−1. This study provides new insights into understand the limitation of interlayer space for ion storage in aqueous media and guides exploration of high‐performance cathode materials.

(C6H15N3)1.3(NH4)1.5H1.5In3SnS8: a layered metal sulfide based on supertetrahedral T2 clusters with photoelectric response and ion exchange properties

“…26 Wide interlayer distances of 1 are due to the introduction of macromolecular organic amines N -(2-aminoethyl) piperazine. It has been shown that the large interlayer is beneficial for accelerating the transport of ions in the lattice, 32 which will endow 1 with some interesting properties.…”

Extrinsic pseudocapacitive ultrathin 2D MoS2 nanoflakes clamped on 1D Sb2S3 nanorods: an advanced heterostructured anode for high-energy ammonium ion hybrid capacitors

“…These values indicate that the majority of the charges were contributed from the rapid reaction kinetics of a surface-controlled process. 60 The exact contributions from the surface- and diffusion-controlled processes were also calculated. Battery-type materials follow a slow charge-storage process due to the diffusion process while capacitive-type materials follow a fast charge-storage process due to the double-layer/surface charge-transfer process.…”

NH4V4O10/rGO Heterostructure with Enlarged (001) Plane Spacing for Aqueous Zinc-Ion Batteries with High Zinc Storage and Highly Reversible Zn2+ Insertion/Extraction

“…After the 10th discharge, the peak of (Zn 3 VO 4 ) 2 appeared and disappeared after charging, further proving that the insertion/extraction of Zn 2+ is reversible after many cycles. The (001) peak intensity of NH 4 V 4 O 10 disappeared after the charging progress, which might be ascribed to the excessive NH 4 + vacancies that cause the deterioration of the crystallinity of NH 4 V 4 O 10 …”

“…+ vacancies that cause the deterioration of the crystallinity of NH 4 V 4 O 10 . 45 The ex situ XPS test was utilized to further investigate the mechanism of electrochemical energy storage. Figure 7c shows the XPS spectra for full discharge and full charge.…”