Organic Ammonium Ion Battery: A New Strategy for a Nonmetallic Ion Energy Storage System

Abstract

Nonmetallic ammonium (NH4+) ion batteries are promising candidates for large‐scale energy storage systems, which have the merit of low molar mass, sustainability, non‐toxicity and non‐dendrite. Herein, for the first time, we introduce the novel organic ammonium ion batteries (OAIBs). Significantly, a manganese‐based Prussian white analogue (noted as MnHCF) as cathode exhibits a reversible capacity of 104 mAh g−1 with 98 % retention over 100 cycles. We further demonstrate the electrochemical performance of the NH4+ ion full cell, which delivers a reversible capacity of 45 mAh g−1 with a broad electrochemical window. Combining ex situ XPS, ex situ XRD results and electrochemical properties, the NH4+ ion storage mechanism of MnHCF in a non‐aqueous electrolyte is clearly revealed. This work verifies the feasibility of employing NH4+ ions as charge carriers in organic energy storage systems and provides new insights for designing organic nonmetallic ion batteries with broad electrochemical windows and high energy density.

Arrayed Heterostructures of MoS2 Nanosheets Anchored TiN Nanowires as Efficient Pseudocapacitive Anodes for Fiber-Shaped Ammonium-Ion Asymmetric Supercapacitors

“…With the further development of artificial intelligence and the Internet of things, portable smart wearable electronic devices will undergo rapid development. − Thus, as a crucial part, the exploitation of flexible wearable energy storage devices and technologies with good safety, cost-effectiveness, environmental friendliness, and long lifetimes will make extraordinary sense. , As an innovative and highly promising energy storage device, fiber-shape supercapacitors have attracted substantial attention ascribed to their light weight, small volume, outstanding flexibility, and weaving. − However, the high cost, limited sources, and side reaction issues have severely affected the extensive applications of metallic cations (for instance, Li + , Na + , K + , Mg 2+ , Zn 2+ , Ca 2+ , and Al 3+ ) in energy storage devices. − Conversely, nonmetallic cationic charge carriers like H + , H 3 O + , and NH 4 + have only acquired small appeal despite their distinct advantages of light molar mass, high ionic conductivity, abundant resources, grid-scale storage, less corrosiveness, and the hydrogen evolution reaction (HER). − …”

Recent Progress in Aqueous Ammonium-Ion Batteries

“…However, a manganese-based Prussian white analogue (MnHCF) was recently obtained that delivered higher capacities for NH 4 + ion storage. 20 Figure 1 a displays the cyclic voltammetry (CV) curve of the MnHCF electrode in a potential range of 0–1 V, revealing major peaks at 0.58, 0.80, 0.60, and 0.45 V. Figure 1 b reveals that the overpotential decreased as the cycling goes on, indicating MnHCF being activated as the cycling continued. The cycling performance of this electrode in Figure 1 c exhibits a capacity retention of 98% from the initial capacity of 104 mAh g –1 at 0.1 A g –1 .…”

“…PBA materials usually show ammonium-ion storage capacities lower than 100 mAh/g. However, a manganese-based Prussian white analogue (MnHCF) was recently obtained that delivered higher capacities for NH 4 + ion storage Figure a displays the cyclic voltammetry (CV) curve of the MnHCF electrode in a potential range of 0–1 V, revealing major peaks at 0.58, 0.80, 0.60, and 0.45 V. Figure b reveals that the overpotential decreased as the cycling goes on, indicating MnHCF being activated as the cycling continued.…”

A metal-free all-organic ammonium-ion battery with low-temperature applications

“…The pioneering work in NH 4 + ion batteries was performed by Yi Cui's group using Prussian blue analogues, i.e., NiHCF and CuHCF mainly because of their open structure and strong structural integrity, delivering a capacity of 55 mA h g −1 and 51.3 mA h g −1 , respectively. 14,15 Various PBAs have been used as cathode materials for NH 4 + ion storage, such as MnHCF, 16 Berlin green, 17 Fe 4 [Fe(CN) 6 ] 3 , 18 K 0.9 Cu 1.3 Fe(CN) 6 , 19 V 1.5 Fe(CN) 6 , 20 NaFe III [Fe II (CN) 6 ], 21 Na 1.45 Fe[Fe(CN) 6 ] 0.93 (ref. 22) and (NH 4 ) 2 Cu[Fe(CN) 6 ].…”

“…4+ ion storage, such as MnHCF,16 Berlin green,17 Fe 4 [Fe(CN) 6 ] 3 , 18 K 0.9 Cu 1.3 Fe(CN) 6 , 19 V 1.5 Fe(CN) 6 , 20 NaFe III [Fe II (CN) 6 ], 21 Na 1.45 Fe[Fe(CN) 6 ] 0.93 (ref. 22) and (NH 4 ) 2 Cu [Fe(CN) 6 ].…”