Achieving Stable Zinc-Ion Storage Performance of Manganese Oxides by Synergistic Engineering of the Interlayer Structure and Interface

Abstract

Manganese oxide is a promising cathode material for rechargeable aqueous zinc-ion batteries (ZIBs). However, the low electronic conductivity and unstable structure evolution of manganese materials often result in poor rate performance and rapid capacity decay. Herein, we design N-doped Na2Mn3O7 (N-NMO) by combining sodium preintercalation and nitridation treatment strategies to stabilize the crystalline structure and reaction interface. Sodium preintercalation not only enlarges the interlayer distance for fast Zn2+ ion diffusion but also serves as a robust pillar to stabilize the crystalline structure during cycling. Meanwhile, the nitridation layer on the surface of Na2Mn3O7 particles is favorable for enhancing the electronic conductivity and inhibiting the cathode dissolution issue during repeated cycling. Consequently, the as-prepared N-NMO exhibits high reversible capacity (300 mAh g–1 at 0.2 A g–1), good rate capability (100 mAh g–1 at 10 A g–1), and outstanding long-term cycling stability (high capacity retention of 78.9% after 550 cycles at 2 A g–1). Considering the facile and simple synthesizing methods, the synergistic engineering of the interlayer structure and interface is expected to provide new opportunities for the development of high-performance Mn-based cathode materials for aqueous ZIBs.

Achieving Ultrahigh-Rate and Low-Temperature Sodium Storage of FePS3 via In Situ Construction of Graphitized Porous N-Doped Carbon

“…39,40 The proportion of pseudocapacitance at different scan rates can be calculated according to i = k 1 v + k 2 v 1/2 , in which k 1 v and k 2 v 1/2 are related to pseudocapacitance and the diffusion process, repspectively. 41,42 The proportion of pseudocapacitance at the scan rates of 0.2−3 mV s −1 were calculated to be 71.6−92.2% (Figure 5c,d), which confirm again that Na + in the FPS/GPNC electrode is a pseudocapacitive-dominated process. Such a high proportion of pseudocapacitance endows FPS/GPNC with superior rate performance.…”

“…The CV curves at 0.2–3 mV s –1 are displayed in Figure a, where the shift of peak with the rise of scan rate means polarization increase. Based on the relation of the peak current and scan speed i = av b , b values can be calculated as 0.97, 0.83, 0.77, and 0.99, revealing that the Na + diffusion in the FPS/GPNC electrode is a pseudocapacitive-dominated process (Figure b). , The proportion of pseudocapacitance at different scan rates can be calculated according to i = k 1 v + k 2 v 1/2 , in which k 1 v and k 2 v 1/2 are related to pseudocapacitance and the diffusion process, repspectively. , The proportion of pseudocapacitance at the scan rates of 0.2–3 mV s –1 were calculated to be 71.6–92.2% (Figure c,d), which confirm again that Na + in the FPS/GPNC electrode is a pseudocapacitive-dominated process. Such a high proportion of pseudocapacitance endows FPS/GPNC with superior rate performance.…”

Methods for Characterizing Intercalation in Aqueous Zinc Ion Battery Cathodes: A Review

“…utilized HRTEM to identify a change in the interlayer spacing of their sodium manganese oxide cathode from 0.574 to 0.543 nm upon the intercalation of nitrogen‐containing species (Figure 3). [ 20 ] Similar to these works, many other studies have also used HRTEM to investigate the interlayer spacing of a layered material, [ 12d–f,13a,c–e,g,15,16,21 ] which often changes upon intercalation, thus acting as indirect evidence for intercalation. HRTEM also allows for directly identifying intercalant atoms in the interlayer spacing, with Chen et al.…”

Challenges and Perspectives for Doping Strategy for Manganese-Based Zinc-ion Battery Cathode

“…MnO 2 was deposited on TiC/C via KMnO 4 decomposition, while N doping was processed by NH 3 treatment at low temperature. Li et al designed a N-doped Na 2 Mn 3 O 7 (N-NMO) in combination with sodium pre-intercalation and nitrification strategies [55]. In the first step, they used a chemical reaction involving KMnO 4 , C 6 H 12 O 6 , and NaKC 4 H 4 O 6 to synthesize rugbytype MnCO 3 particles as precursors.…”

“…Wang et al employed a mechanical cell grinder for doping Na + into MnO 2 and obtained a Na 0.44 MnO 2 cathode, which had a large specific surface area[67]. In 2022, Li et al reported a N-doped Na 2 Mn 3 O 7 cathode that displayed a capacity of 300 mAh•g −1 at a current density of 0.2 A•g −1 , which even retained a capacity of 100 mAh•g −1 at 10 A•g −1[55]. The modification principle was that the doping of sodium ions could enlarge the interlayer spacing and serve as a pillar to stabilize the host structure.…”