Rechargeable aqueous Zn-ion batteries are attractive cheap, safe and green energy storage technologies but are bottlenecked by limitation in high-capacity cathode and compatible electrolyte to achieve satisfactory cyclability. Here we report the application of nonstoichiometric ZnMnO/carbon composite as a new Zn-insertion cathode material in aqueous Zn(CFSO) electrolyte. In 3 M Zn(CFSO) solution that enables ∼100% Zn plating/stripping efficiency with long-term stability and suppresses Mn dissolution, the spinel/carbon hybrid exhibits a reversible capacity of 150 mAh g and a capacity retention of 94% over 500 cycles at a high rate of 500 mA g. The remarkable electrode performance results from the facile charge transfer and Zn insertion in the structurally robust spinel featuring small particle size and abundant cation vacancies, as evidenced by combined electrochemical measurements, XRD, Raman, synchrotron X-ray absorption spectroscopy, FTIR, and NMR analysis. The results would enlighten and promote the use of cation-defective spinel compounds and trifluoromethanesulfonic electrolyte to develop high-performance rechargeable zinc batteries.
Electrochemical water splitting is a promising technology for sustainable conversion, storage, and transport of hydrogen energy. Searching for earth‐abundant hydrogen/oxygen evolution reaction (HER/OER) electrocatalysts with high activity and durability to replace noble‐metal‐based catalysts plays paramount importance in the scalable application of water electrolysis. A freestanding electrode architecture is highly attractive as compared to the conventional coated powdery form because of enhanced kinetics and stability. Herein, recent progress in developing transition‐metal‐based HER/OER electrocatalytic materials is reviewed with selected examples of chalcogenides, phosphides, carbides, nitrides, alloys, phosphates, oxides, hydroxides, and oxyhydroxides. Focusing on self‐supported electrodes, the latest advances in their structural design, controllable synthesis, mechanistic understanding, and strategies for performance enhancement are presented. Remaining challenges and future perspectives for the further development of self‐supported electrocatalysts are also discussed.
We report an aqueous Zn−V 2 O 5 battery chemistry employing commercial V 2 O 5 cathode, Zn anode, and 3 M Zn(CF 3 SO 3 ) 2 electrolyte. We elucidate the Zn-storage mechanism in the V 2 O 5 cathode to be that hydrated Zn 2+ can reversibly (de)intercalate through the layered structure. The function of the cointercalated H 2 O is revealed to be shielding the electrostatic interactions between Zn 2+ and the host framework, accounting for the enhanced kinetics. In addition, the pristine bulk V 2 O 5 gradually evolves into porous nanosheets upon cycling, providing more active sites for Zn 2+ storage and thus rendering an initial capacity increase. As a consequence, a reversible capacity of 470 mAh g −1 at 0.2 A g −1 and a long-term cyclability with 91.1% capacity rentention over 4000 cycles at 5 A g −1 are achieved. The combination of the good battery performance, safety, scalable materials synthesis, and facile cell assembly indicates this aqueous Zn−V 2 O 5 system is promising for stationary grid storage applications.
High-performance rechargeable Na/FeS2batteries showing only the intercalation reaction are obtained by selecting a NaSO3CF3/diglyme electrolyte and tuning the cut-off voltage to 0.8 V.
The development of highly active and stable oxygen evolution reaction (OER) electrocatalysts is crucial for improving the efficiency of water splitting and metal-air battery devices. Herein, an efficient strategy is demonstrated for making the oxygen vacancies dominated cobalt-nickel sulfide interface porous nanowires (NiS /CoS -O NWs) for boosting OER catalysis through in situ electrochemical reaction of NiS /CoS interface NWs. Because of the abundant oxygen vacancies and interface porous nanowires structure, they can catalyze the OER efficiently with a low overpotential of 235 mV at j = 10 mA cm and remarkable long-term stability in 1.0 m KOH. The home-made rechargeable portable Zn-air batteries by using NiS /CoS -O NWs as the air-cathode display a very high open-circuit voltage of 1.49 V, which can maintain for more than 30 h. Most importantly, a highly efficient self-driven water splitting device is designed with NiS /CoS -O NWs as both anode and cathode, powered by two-series-connected NiS /CoS -O NWs-based portable Zn-air batteries. The present work opens a new way for designing oxygen vacancies dominated interface nanowires as highly efficient multifunctional electrocatalysts for electrochemical reactions and renewable energy devices.
The development of highly efficient bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is crucial for improving the efficiency of the Zn-air battery. Herein, we report porous NiO/CoN interface nanowire arrays (PINWs) with both oxygen vacancies and a strongly interconnected nanointerface between NiO and CoN domains for promoting the electrocatalytic performance and stability for OER and ORR. Extended X-ray absorption fine structure spectroscopy, electron spin resonance, and high-resolution transmission electron microscopy investigations demonstrate that the decrease of the coordination number for cobalt, the enhanced oxygen vacancies on the NiO/CoN nanointerface, and strongly coupled nanointerface between NiO and CoN domains are responsible for the good bifunctional electrocatalytic performance of NiO/CoN PINWs. The primary Zn-air batteries, using NiO/CoN PINWs as an air-cathode, display an open-circuit potential of 1.46 V, a high power density of 79.6 mW cm, and an energy density of 945 Wh kg. The three-series solid batteries fabricated by NiO/CoN PINWs can support a timer to work for more than 12 h. This work demonstrates the importance of interface coupling and oxygen vacancies in the development of high-performance Zn-air batteries.
Cobalt-containing spinel oxides are promising electrocatalysts for the oxygen evolution reaction (OER) owing to their remarkable activity and durability. However, the activity still needs further improvement and related fundamentals remain untouched. The fact that spinel oxides tend to form cation deficiencies can differentiate their electrocatalysis from other oxide materials, for example, the most studied oxygen-deficient perovskites. Here, a systematic study of spinel ZnFe Co O oxides (x = 0-2.0) toward the OER is presented and a highly active catalyst superior to benchmark IrO is developed. The distinctive OER activity is found to be dominated by the metal-oxygen covalency and an enlarged CoO covalency by 10-30 at% Fe substitution is responsible for the activity enhancement. While the pH-dependent OER activity of ZnFe Co O (the optimal one) indicates decoupled proton-electron transfers during the OER, the involvement of lattice oxygen is not considered as a favorable route because of the downshifted O p-band center relative to Fermi level governed by the spinel's cation deficient nature.
Two 3d-4f heterometallic coordination polymers {[Ln(PDA)3Mn1.5(H2O)3].3.25H2O}infinity with 1D channels were synthesized under hydrothermal conditions (PDA = pyridine-2,6-dicarboxylic acid; Ln = Eu (1); Ln = Tb (2)). The emission intensities of 1 and 2 increased significantly upon addition of Zn2+, while the introduction of other metal ions caused the intensity to be either unchanged or weakened. The case implies that 1 and 2 may be used as luminescent probes of Zn2+.
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