Femtosecond Laser‐Etched MXene Microsupercapacitors with Double‐Side Configuration via Arbitrary On‐ and Through‐Substrate Connections

The capacitance of microsupercapacitors (MSCs) can double if both sides of substrates are used to construct MSCs. Nevertheless, achieving electric connections of MSCs through substrates is a challenge due to the difficulty in precisely positioning each MSC couple that has two of the same MSCs units on two sides. In this work, taking advantage of the synchronous etching on both sides of transparent polyethylene terephthalate substrates by femtosecond laser pulses, a double‐sided configuration is attained with high precision in the alignment of back‐to‐back MSC couples and versatile double‐side MSCs are realized via arbitrary on‐ and through‐substrate connections of MXene MSC units. The MXene double‐side MSC fabricated by the series connection of 12 spiral pattern MXene MSC units with interdigital electrodes of 10 μm width interspace can output a large working voltage of 7.2 V. Additionally, femtosecond laser etching brings the transformation of MXene into titania near‐etched edges with a lateral distance less than 1 µm. Such a small laser‐affected area has little influence on the capacitive performance, which is one of advantages for femtosecond laser over conventional lasers. This research is valuable for one‐step manufacturing of highly integrated MSCs in the field of miniaturized energy storage systems.     

Spontaneous Atomic Ruthenium Doping in Mo2CTX MXene Defects Enhances Electrocatalytic Activity for the Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) process usually suffers extremely low Faradaic efficiency and ammonia yields due to sluggish N?N dissociation. Herein, single‐atomic ruthenium modified Mo₂CT_X MXene nanosheets as an efficient electrocatalyst for nitrogen fixation at ambient conditions are reported. The catalyst achieves a Faradaic efficiency of 25.77% and ammonia yield rate of 40.57 µg h^?1 mg^?1 at ‐0.3 V versus the reversible hydrogen electrode in 0.5 m K₂SO₄ solution. Operando X‐ray absorption spectroscopy studies and density functional theory calculations reveal that single‐atomic Ru anchored on MXene nanosheets act as important electron back‐donation centers for N₂ activation, which can not only promote nitrogen adsorption and activation behavior of the catalyst, but also lower the thermodynamic energy barrier of the first hydrogenation step. This work opens up a promising avenue to manipulate catalytic performance of electrocatalysts utilizing an atomic‐level engineering strategy.     

High‐Efficiency Thermoelectric Power Generation Enabled by Homogeneous Incorporation of MXene in (Bi,Sb)2Te3 Matrix

The (Bi,Sb)₂Te₃ (BST) compounds have long been considered as the benchmark of thermoelectric (TE) materials near room temperature especially for refrigeration. However, their unsatisfactory TE performances in wide‐temperature range severely restrict the large‐scale applications for power generation. Here, using a self‐assembly protocol to deliver a homogeneous dispersion of 2D inclusion in matrix, the first evidence is shown that incorporation of MXene (Ti₃C₂T_x) into BST can simultaneously achieve the improved power factor and greatly reduced thermal conductivity. The oxygen‐terminated Ti₃C₂T_x with proper work function leads to highly increased electrical conductivity via hole injection and retained Seebeck coefficient due to the energy barrier scattering. Meanwhile, the alignment of Ti₃C₂T_x with the layered structure significantly suppresses the phonon transport, resulting in higher interfacial thermal resistance. Accordingly, a peak ZT of up to 1.3 and an average ZT value of 1.23 from 300 to 475 K are realized for the 1 vol% Ti₃C₂T_x/BST composite. Combined with the high‐performance composite and rational device design, a record‐high thermoelectric conversion efficiency of up to 7.8% is obtained under a temperature gradient of 237 K. These findings provide a robust and scalable protocol to incorporate MXene as a versatile 2D inclusion for improving the overall performance of TE materials toward high energy‐conversion efficiency.     

Enhanced Rate Capability of Ion‐Accessible Ti3C2Tx‐NbN Hybrid Electrodes

Although 2D Ti₃C₂T_x is a good candidate for supercapacitors, the restacking of nanosheets hinders the ion transport significantly at high scan rates, especially under practical mass loading (>10 mg cm^?2) and thickness (tens of microns). Here, Ti₃C₂T_x‐NbN hybrid film is designed by self‐assembling Ti₃C₂T_x with 2D arrays of NbN nanocrystals. Working as an interlayer spacer of Ti₃C₂T_x, NbN facilitates the ion penetration through its 2D porous structure; even at extremely high scan rates. The hybrid film shows a thickness‐independent rate performance (almost the same rate capabilities from 2 to 20 000 mV s^?1) for 3 and 50 µm thick electrodes. Even a 109 µm thick Ti₃C₂T_x‐NbN electrode shows a better rate performance than 25 µm thick pure Ti₃C₂T_x electrodes. This method may pave a way to controlling ion transport in electrodes composed of 2D conductive materials, which have potential applications in high‐rate energy storage and beyond.     

In Situ Electrochemical Synthesis of MXenes without Acid/Alkali Usage in/for an Aqueous Zinc Ion Battery

The traditional method to fabricate a MXene based energy storage device starts from etching MAX phase particles with dangerous acid/alkali etchants to MXenes, followed by device assembly. This is a multistep protocol and is not environmentally friendly. Herein, an all‐in‐one protocol is proposed to integrate synthesis and battery fabrication of MXene. By choosing a special F‐rich electrolyte, MAX V₂AlC is directly exfoliated inside a battery and the obtained V₂CT_X MXene is in situ used to achieve an excellent battery performance. This is a one‐step process with all reactions inside the cell, avoiding any contamination to external environments. Through the lifetime, the device experiences three stages of exfoliation, electrode oxidation, and redox of V₂O₅. While the electrode is changing, the device can always be used as a battery and the performance is continuously enhanced. The resulting aqueous zinc ion battery achieves outstanding cycling stability (4000 cycles) and rate performance (97.5 mAh g^?1 at 64 A g^?1), distinct from all reported aqueous MXene‐based counterparts with pseudo‐capacitive properties, and outperforming most vanadium‐based zinc ion batteries with high capacity. This work sheds light on the green synthesis of MXenes, provides an all‐in‐one protocol for MXene devices, and extends MXenes’ application in the aqueous energy storage field.     

Nanoscale Elastic Changes in 2D Ti3C2Tx (MXene) Pseudocapacitive Electrodes

Designing sustainable electrodes for next generation energy storage devices relies on the understanding of their fundamental properties at the nanoscale, including the comprehension of ions insertion into the electrode and their interactions with the active material. One consequence of ion storage is the change in the electrode volume resulting in mechanical strain and stress that can strongly affect the cycle life. Therefore, it is important to understand the changes of dimensions and mechanical properties occurring during electrochemical reactions. While the characterization of mechanical properties via macroscopic measurements is well documented, in situ characterization of their evolution has never been achieved at the nanoscale. It is reported here with in situ imaging, combined with density functional theory of the elastic changes of a 2D titanium carbide (Ti₃C₂T_x) based electrode in direction normal to the basal plane (electrode surface) during alkaline cation intercalation/extraction. 2D carbides, known as MXenes, are promising new materials for supercapacitors and various kinds of batteries, and understanding the coupling between their mechanical and electrochemical properties is therefore necessary. The results show a strong correlation between the cations content and the out‐of‐plane elastic modulus. This strategy enables identifying the preferential intercalation pathways within a single particle, which is important for understanding ionic transport in these materials.     

MXene‐Contacted Silicon Solar Cells with 11.5% Efficiency

MXene, a new class of 2D materials, has gained significant attention owing to its attractive electrical conductivity, tunable work function, and metallic nature for wide range of applications. Herein, delaminated few layered Ti₃C₂T_x MXene contacted Si solar cells with a maximum power conversion efficiency (PCE) of ≈11.5% under AM1.5G illumination are demonstrated. The formation of an Ohmic junction of the metallic MXene to n⁺‐Si surface efficiently extracts the photogenerated electrons from n⁺np⁺‐Si, decreases the contact resistance, and suppresses the charge carrier recombination, giving rise to excellent open‐circuit voltage and short‐circuit current density. The rapid thermal annealing process further improves the electrical contact between Ti₃C₂T_x MXene and n⁺‐Si surface by reducing sheet resistance, increasing electrical conductivity, and decreasing cell series resistance, thus leading to a remarkable improvement in fill factor and overall PCE. The work demonstrated here can be extended to other MXene compositions as potential electrodes for developing highly performing solar cells.     

All Pseudocapacitive MXene‐RuO2 Asymmetric Supercapacitors

2D transition metal carbides and nitrides, known as MXenes, are an emerging class of 2D materials with a wide spectrum of potential applications, in particular in electrochemical energy storage. The hydrophilicity of MXenes combined with their metallic conductivity and surface redox reactions is the key for high‐rate pseudocapacitive energy storage in MXene electrodes. However, symmetric MXene supercapacitors have a limited voltage window of around 0.6 V due to possible oxidation at high anodic potentials. In this study, the fact that titanium carbide MXene (Ti₃C₂T_x) can operate at negative potentials in acidic electrolyte is exploited, to design an all‐pseudocapacitive asymmetric device by combining it with a ruthenium oxide (RuO₂) positive electrode. This asymmetric device operates at a voltage window of 1.5 V, which is about two times wider than the operating voltage window of symmetric MXene supercapacitors, and is the widest voltage window reported to date for MXene‐based supercapacitors. The complementary working potential windows of MXene and RuO₂, along with proton‐induced pseudocapacitance, significantly enhance the device performance. As a result, the asymmetric devices can deliver an energy density of 37 µW h cm^?2 at a power density of 40 mW cm^?2, with 86% capacitance retention after 20 000 charge–discharge cycles. These results show that pseudocapacitive negative MXene electrodes can potentially replace carbon‐based materials in asymmetric electrochemical capacitors, leading to an increased energy density.