Manipulating anion intercalation enables a high-voltage aqueous dual ion battery

Guo

Advanced Energy Materials

et al. 2022

Self Cite

121

reformed hydrogen as feedstock under harsh conditions. [3] Ambient electrocatalytic N 2 reduction reaction (NRR) has emerged as an attractive alternative for NH 3 production, which however suffers from unsatisfactory Faradaic efficiencies (FE) (mostly <50%) and very low NH 3 partial current densities (mostly <1 mA cm -2 ) due to extremely stable triple NN bond (941 kJ mol -1 ) and low N 2 solubility. [4,5] Nitrate reduction into NH 3 (NO 3 -RR) is considered as a promising alternative with large attainable yields owing to the high solubility of NO 3 and low NO bond energy (204 kJ mol -1 ). [6] Furthermore, NO 3 is one of the most widespread groundwater pollutants in the world due to the discharge of industrial wastewater, livestock excrements, and chemical fertilizers, imposing a threat to the health of human beings. [7] Therefore, it is highly attractive to harness NO 3 contaminants to produce the value-added NH 3 from the energy and environmental perspectives.In addition to the chemicals, electricity is one other key pillar of human society. [8][9][10][11][12][13][14][15][16] Notably, the NO 3 -RR involves proton-assisted eightelectron transfer process and its equilibrium potential is 0.69 V versus the reversible hydrogen electrode (RHE), higher than the 0.4 V of the oxygen reduction reaction in Zn-air/oxygen batteries. [17] It is thus highly attractive to combine the NO 3 -RRbased cathode with metal anode as a galvanic cell for electricity production. Such metal-NO 3 battery as a "killing three birds with one stone" strategy is capable of energy supply, ammonia production, and removal of pollutant in ground water. As some possible byproducts such as nitrite and hydrazine may lower the efficiency of such battery, catalyst cathodes with high NH 3 selectivity is highly desired for practical use. [18][19][20] First row transition metal phosphides, as alloy materials of metal and phosphorus, are active catalysts in hydrotreating (HDX, X = S, O, N) and hydrogenation reactions. [21,22] The metal centers in phosphides with partial positive charge can adsorb nitrate and nitrite anions effectively while the partial negative charge centers, i.e., phosphorus, are the proton-acceptor centers. [23] Further, heteroatom doping can well modulate the electronic structure of the catalyst and boost the catalytic activity. [24] The The electrocatalytic nitrate reduction reaction (NO 3 -RR) to ammonia (NH 3 ) offers a promising alternative approach for NH 3 production and nitratebased voltaic cells which can deliver both electricity and NH 3 as products, are also highly attractive. However, nitrate-to-NH 3 conversion involves a proton-assisted multiple-electron transfer process with considerable kinetic barrier, underlying the need for efficient catalysts for the NO 3 -RR. A Zn-nitrate battery is reported to enable a "killing three birds with one stone" strategy for energy supply, ammonia production and removal of pollutants with the iron doped nickel phosphide (Fe/Ni 2 P) as a NO 3 -RR catalyst electrode. Iron doping induces a d...

Section: (4 Of 8)mentioning

confidence: 99%

Efficient Ammonia Electrosynthesis and Energy Conversion through a Zn‐Nitrate Battery by Iron Doping Engineered Nickel Phosphide Catalyst

Guo

Advanced Energy Materials

et al. 2022

Self Cite

121

“…

…”

mentioning

confidence: 99%

A MOF‐Derivative Decorated Hierarchical Porous Host Enabling Ultrahigh Rates and Superior Long‐Term Cycling of Dendrite‐Free Zn Metal Anodes

et al. 2022

cell design have presented numerous safety hazards and economic challenges, [3][4][5] which make LIBs less suitable for largescale applications. Compared with organic LIBs, aqueous rechargeable Zn-ion batteries (ZIBs) equipped with nonflammable and highly ion conductive aqueous electrolytes are highly desirable. They benefit from a high theoretical capacity (a gravimetric capacity of 820 mAh g −1 and a volumetric capacity of 5855 mAh cm −3 ) and a low plating/stripping potential (−0.76 V vs standard hydrogen electrode), as well as a high natural abundance of metallic Zn. [6][7][8] Unfortunately, the uncontrolled formation of dendrites, undesired side reactions (e.g., corrosion, hydrogen evolution, and by-product formation), and huge volume variation during repeated Zn deposition-dissolution processes of the host-less metallic Zn anode not only limit the efficiency of plating and stripping, but also result in a remarkably short lifespan, or even internal short-circuiting. [9][10][11] In order to address the issues mentioned above, several strategies have been proposed to regulate the Zn plating/stripping behaviors for stable Zn metal batteries, including surface modification, [12][13][14] electrolyte optimization, [15][16][17] and electrode structural design. [18][19][20] For instance, an ultrathin MXene layer and glucose have been used as an artificial layer and a multifunctional electrolyte additive to stabilize Zn metal anodes, Aqueous Zn metal batteries have attracted much attention due to their high intrinsic capacity, high safety, and low cost. Nevertheless, uncontrollable dendrite growth and adverse side reactions of Zn anodes seriously hinder their further application. Herein, a three-dimensional (3D) porous graphene-carbon nanotubes scaffold decorated with metal-organic framework derived ZnO/C nanoparticles (3D-ZGC) is fabricated as the host for dendrite-free Zn-metal composite anodes. The zincophilic ZnO/C nanoparticles act as preferred deposition sites with low nucleation barriers to induce homogeneous Zn deposition. The mechanically robust 3D scaffold with high conductivity not only suppresses the formation of dendritic Zn by reducing the local current density and homogenizing Zn 2+ ion flux, but also inhibits volume changes during the long-term plating/stripping process. As a result, the 3D-ZGC composite anodes afford unprecedented Zn plating-stripping stability at an ultrahigh current density of 20 mA cm -2 for 1500 cycles with low overpotential (<65 mV) when used in a symmetric cell. When coupled with MnO 2 cathodes, the assembled Zn@3D-ZGC//MnO 2 full batteries deliver an enhanced cycling stability for up to 6000 cycles at 2000 mA g -1 , demonstrating the potential of the 3D-ZGC composite anode for advanced Zn metal batteries.

“…The reversible intercalation of FSI À is also confirmed by the ex situ Raman spectroscopy, in which a shoulder peak with a higher Raman shift value for G peak appears after charging, and recovers after fully discharged (Figure 2c). [16] Furthermore, after 400 cycles in the 0-2.5 V voltage range, a discharge capacity of 41.4 mAh g À 1 can be retained, showing good cycling stability (Figure 2d). The selected cycles (100th, 200th, 300th, and 400th) have overlapped plateaus, indicating good cycling stability and small polarization (Figure 2e).…”

Section: Forschungsartikelmentioning

confidence: 96%

Concentrated Electrolyte for High‐Performance Ca‐Ion Battery Based on Organic Anode and Graphite Cathode

Han

et al. 2022

Angewandte Chemie

Due to the large abundance, low redox potential, and multivalent properties of calcium (Ca), Ca-ion batteries (CIBs) show promising prospects for energy storage applications. However, current research on CIBs faces the challenges of unsatisfactory cycling stability and capacity, mainly restricted by the lack of suitable electrolytes and electrode materials. Herein, we firstly developed a 3.5 m concentrated electrolyte with a calcium bis(fluorosulfonyl)imide (Ca(FSI) 2 ) salt dissolved in carbonate solvents. This electrolyte significantly improved the intercalation capacity for anions in the graphite cathode and contributed to the reversible insertion of Ca 2 + in the organic anode. By combining this concentrated electrolyte with the low-cost and environmentally friendly graphite cathode and organic anode, the assembled Ca-based dual-ion battery (Ca-DIB) exhibits 75.4 mAh g À 1 specific discharge capacity at 100 mA g À 1 and 84.7 % capacity retention over 350 cycles, among the best results known for CIBs.