Progress in the direct catalytic conversion of methane to fuels and chemicals

Exploration of alternative energy storage systems has been more than necessary in view of the supply risks haunting lithium-ion batteries. Among various alternative electrochemical energy storage devices, sodium-ion battery outstands with advantages of cost-effectiveness and comparable energy density with lithium-ion batteries. Thanks to the similar electrochemical mechanism, the research and development of lithium-ion batteries have forged a solid foundation for sodium-ion battery explorations. Advancements in sodium-ion batteries have been witnessed in terms of superior electrochemical performance and broader application scenarios. Here, the strategies adopted to optimize the battery components (cathode, anode, electrolyte, separator, binder, current collector, etc.) and the cost, safety, and commercialization issues in sodium-ion batteries are summarized and discussed. Based on these optimization strategies, assembly of functional (flexible, stretchable, self-healable, and self-chargeable) and integrated sodium-ion batteries (−actuators, −sensors, electrochromic, etc.) have been realized. Despite these achievements, challenges including energy density, scalability, trade-off between energy density and functionality, cost, etc. are to be addressed for sodium-ion battery commercialization. This review aims at providing an overview of the up-to-date achievements in sodium-ion batteries and serves to inspire more efforts in designing upgraded sodium-ion batteries. 

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/eem2.12633

Optimization Strategies Toward Functional Sodium‐Ion Batteries

Methane aromatisation based upon elementary steps: Kinetic and catalyst descriptors

This paper presents an experimental and modeling study of methane dehydroaromatization (MDA) chemistry using a bifunctional 6 wt % Mo/HZSM-5 catalyst in an isothermal laboratory-scale packed-bed configuration. The reported measurements include methane conversion and product yields and selectivities as a function of temperature and flow rates (space velocity). The modeling is particularly concerned with developing and validating a microscopically reversible 54-step detailed reaction mechanism. The reaction mechanism is validated via direct comparison with the measured packed-bed performance. Although the operating conditions for the measurements are relatively limited, the detailed reaction mechanism is expected to have much wider predictive capability.

Catalytic Chemistry for Methane Dehydroaromatization (MDA) on a Bifunctional Mo/HZSM-5 Catalyst in a Packed Bed

Aqueous zinc ion batteries have received widespread attention due to their merits of high safety, high theoretical specific capacity, low cost, and environmental benignity. Nevertheless, the irreversible issues of Zn anode deriving from side reactions and dendrite growth have hindered its commercialization in large-scale energy storage systems. Herein, a zinc phosphate tetrahydrate (Zn3 (PO4 )2 ·4H2 O, ZnPO) coating layer is in situ formed on the bare Zn by spontaneous redox reactions at room temperature to tackle the above issues. Particularly, the dense and brick-like ZnPO layer can effectively separate the anode surface from the aqueous electrolyte, thus suppressing the serious side reactions. Moreover, the ZnPO layer with high ionic conductivity, high Zn2+ transference number, and low nucleation barrier permits rapid Zn2+ transport and enables uniform Zn deposition, ensuring dendrite-free Zn deposition. As a result, the ZnPO@Zn symmetric battery achieves a high Coulombic efficiency of 99.8% and displays ultrahigh cycle stability over 6000 h (> 8 months), far surpassing its counterparts. Furthermore, the ZnPO@Zn||MnO2 full battery exhibits excellent electrochemical performances. Therefore, this work provides a new reference for simple and large-scale preparation of highly reversible Zn metal anodes, and has great potential for practical applications.

In Situ Spontaneous Construction of Zinc Phosphate Coating Layer Toward Highly Reversible Zinc Metal Anodes.

The aqueous zinc-ion hybrid capacitors (ZIHCs) have promising applications for large-scale energy storage due to high safety and low cost. However, the ZIHCs suffer from the poor cycling performance and the inability of the device to operate at freezing point. Herein, we designed an integrated device architecture consisting of a copper-tin nanowires (Cu-Sn NWs) array loaded zinc substrate with 3D pro-zinc channels assembled in-situ with a freeze-resistant electrolyte to realize flexible ZIHCs based on a dendrite free zinc anode. The Cu-Sn NWs with extremely low zinc nucleation overpotential induce uniform zinc deposition by homogenizing the electric field, while the resulting 3D nanowire array scaffold with ample internal space buffers the volume changes during the stripping/plating process. As-fabricated Zn-loaded substrate shows an extremely low voltage polarization of 23 mV and the outstanding ability to stably stripping/plating for 1200 h at 5 mA cm−1. Furthermore, the as-assembled flexible ZIHC is outstanding cycling performance (nearly 85.5% capacitance retention after 10,000 cycles at –20 °C) by in-situ polymerization of anti-freeze acrylamide-based composite hydrogel electrolyte on the zinc-loaded substrate. The strategy helps to stimulate the application of high-performance dendrite-free flexible energy-storage devices in cold environment. 

Zincophile channel adjustment realizes dendrite-free zinc anode for low-temperature zinc-ion capacitors

Stretchable sodium-ion capacitors (SSICs) are promising energy storage devices for wearable electronic devices, and the development bottleneck is the realization of stretchable battery-type electrodes with desirable electrochemical properties during dynamic deformation. Herein, we find that electrostatic modification of acidified carbon nanotubes with polyamines can introduce active sites and modulate the surface pH microenvironment, thereby developing a route to realize the in situ coaxial nanometerization of sodium titanate (nCNT@NTO). The nCNT@NTO anode material has a fast Na+ transport and the high capacitive contribution, which can deliver a high specific capacity (206.5 mA h g-1 at 0.1 A g-1) and high rate performance (maintain 51% capacity at 10 A g-1), and the ideal cycle stability (∼93% capacity retention after 1000 cycles at 5 A g-1). In addition, acrylate-rubber with high stickiness and stretchability are served as the elastic matrix both of the stretchable electrodes and quasi-solid-state electrolytes, which endows strong adhesion between electrodes and electrolytes. Thus, the accordingly assembled SSIC delivers high energy density of 8.8 mW h cm-3 (at a power density of 0.024 W cm-3), and excellent deformation stability (89% capacitance retention after 500 stretching cycles under 100% strain).

Stretchable sodium-ion capacitors based on coaxial CNT supported Na2Ti3O7 with high capacitance contribution.

Sodium-ion capacitors (SICs) bear the advantages of secondary batteries and supercapacitors and are regarded as promising energy-storage devices. However, the matching of the respective Na+-transfer kinetics of the anode and the cathode and the low energy density are still a challenge. Herein, to achieve a high-capacity cathode, 2D V2C MXene nanosheets were introduced into γ-ray-reduced graphene oxide (γ-rGO), and the γ-rGO/V2C MXene foam (GMF) was fabricated. The GMF provides a high specific capacitance of 391.4 mF cm–2 (130.5 F g–1) at a high current density of 60 mA cm–2 (20 A g–1). Meanwhile, the structure-directing strategy combining multiple nanocarbon composites accelerates the Na+-transfer kinetics of sodium titanate (NTO). The as-fabricated CNT film-supported sodium titanate nanowires encapsulated by the graphene (CNTF@NTO-G) anode deliver a specific capacity of 109 mA h g–1 at a high current density of 10 A g–1. As a result, the assembled quasi-solid-state SIC displays an energy density of 5.61 mW h cm–3 (56.1 W h kg–1) at a power density of 1 W cm–3 (10 kW kg–1) with excellent cycle stability (87.3% capacitance retention after 10,000 cycles). 

High-Capacitance γ-rGO/MXene Cathode and Rapid Na+-Transfer Dynamics Sodium Titanate Anode for a Quasi-Solid-State Sodium-Ion Capacitor

Intrinsic kinetics of methane aromatization under non-oxidative conditions over modified Mo/HZSM-5 catalysts

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Zincophile channel adjustment realizes dendrite-free zinc anode for low-temperature zinc-ion capacitors

Stretchable sodium-ion capacitors based on coaxial CNT supported Na2Ti3O7 with high capacitance contribution.

High-Capacitance γ-rGO/MXene Cathode and Rapid Na+-Transfer Dynamics Sodium Titanate Anode for a Quasi-Solid-State Sodium-Ion Capacitor

Intrinsic kinetics of methane aromatization under non-oxidative conditions over modified Mo/HZSM-5 catalysts