Laser-Scribed Battery Electrodes for Ultrafast Zinc-Ion Energy Storage.

Aqueous Zn batteries are promising for large-scale energy storage but are plagued by the lack of high-performance cathode materials that enable high specific capacity, ultrafast charging, and outstanding cycling stability. Here, a laser-scribed nano-vanadium oxide (LNVO) cathode is designed that can simultaneously achieve these properties. The material stores charge through Faradaic redox reactions on/near the surface at fast rates owing to the small grain size of vanadium oxide and interpenetrating 3D graphene network, displaying a surface-controlled capacity contribution (90%-98%). Multiple characterization techniques unambiguously reveal that zinc and hydronium ions co-insert with minimal lattice change upon cycling. It is demonstrated that a high specific capacity of 553 mAh g-1 is achieved at 0.1 A g-1, and an impressive 264 mAh g-1 capacity is retained at 100 A g-1 within 10 s, showing excellent rate capability. The LNVO/Zn can also reach >90% capacity retention after 3000 cycles at a high rate of 30 A g-1, as well as achieving both high energy (369 Wh kg-1) and power densities (56306 W kg-1). Moreover, the LNVO cathode retains its excellent cycling performance when integrated into quasi-solid-state pouch cells, further demonstrating mechanical stability and its potential for practical application in wearable and grid-scale applications.

A nanoengineered vanadium oxide composite as a high-performance anode for aqueous Li-ion hybrid batteries.

Aqueous lithium-ion batteries (LIBs) have received increasing attention as a promising solution for stationary energy storage systems due to their low environmental impact, non-flammability and low cost. Despite recent progress in electrolyte development and cathode manufacturing, the lack of anode materials with high specific capacity presents difficult challenges for a wide range of applications. In this study, we propose a novel synthetic strategy to fabricate a pseudocapacitive V2O5/graphene composite as a highly functional anode material for aqueous LIBs. The designed synthesis combines a fast laser-scribing step with controlled calcination to tune the morphology and oxidation state of the electrochemically active vanadium oxide species while obtaining a highly conductive graphene scaffold. The optimized V2O5/graphene anode shows an outstanding specific capacity of 158 mA h g-1 in three-electrode measurements. When the V2O5/graphene anode is paired with an LiMn2O4 cathode, the charge storage mechanism of the full cell is revealed to be dominantly surface-controlled, resulting in remarkable rate performance. Specifically, the full cell can reach a specific capacity of 151 and 107 mA h (g anode)-1 at C/6 and 3C, respectively. Moreover, this hybrid battery can achieve a high power density and an energy density of 650 W kg-1 at 15.6 W h kg-1 and 81.5 W h kg-1 at 13.6 W kg-1, respectively, outperforming most aqueous LIBs reported in the literature. This innovative strategy provides a pathway to incorporate pseudocapacitive electrodes for improving aqueous lithium-ion storage systems, enabling safe operation of large-scale energy storage without compromising their electrochemical performance.

A Rapid, Scalable Laser-Scribing Process to Prepare Si/Graphene Composites for Lithium-Ion Batteries.

Silicon has gained significant attention as a lithium-ion battery anode material due to its high theoretical capacity compared to conventional graphite. Unfortunately, silicon anodes suffer from poor cycling performance caused by their extreme volume change during lithiation and de-lithiation. Compositing silicon particles with 2D carbon materials, such as graphene, can help mitigate this problem. However, an unaddressed challenge remains: a simple, inexpensive synthesis of Si/graphene composites. Here, a one-step laser-scribing method is proposed as a straightforward, rapid (≈3 min), scalable, and less-energy-consuming (≈5 W for a few minutes under air) process to prepare Si/laser-scribed graphene (LSG) composites. In this research, two types of Si particles, Si nanoparticles (SiNPs) and Si microparticles (SiMPs), are used. The rate performance is improved after laser scribing: SiNP/LSG retains 827.6 mAh g-1 at 2.0 A gSi+C -1 , while SiNP/GO (before laser scribing) retains only 463.8 mAh g-1 . This can be attributed to the fast ion transport within the well-exfoliated 3D graphene network formed by laser scribing. The cyclability is also improved: SiNP/LSG retains 88.3% capacity after 100 cycles at 2.0 A gSi+C -1 , while SiNP/GO retains only 57.0%. The same trend is found for SiMPs: the SiMP/LSG shows better rate and cycling performance than SiMP/GO composites.

Labile Coordination Interphase for Regulating Lean Ion Dynamics in Reversible Zn Batteries.

Rechargeability in zinc (Zn) batteries is limited by anode irreversibility. The practical lean electrolytes exacerbate the issue, compromising the cost benefits of zinc batteries for large-scale energy storage. In this study, a zinc-coordinated interphase is developed to avoid chemical corrosion and stabilize zinc anodes. The interphase promotes Zn2+ ions to selectively bind with histidine and carboxylate ligands, creating a coordination environment with high affinity and fast diffusion due to thermodynamic stability and kinetic lability. Experiments and simulations indicate that interphase regulates dendrite-free electrodeposition and reduces side reactions. Implementing such labile coordination interphase results in increased cycling at 20 mA cm-2 and high reversibility of dendrite-free zinc plating/stripping for over 200 hours. A Zn||LiMn2 O4 cell with 74.7 mWh g-1 energy density and 99.7% Coulombic efficiency after 500 cycles realized enhanced reversibility using the labile coordination interphase. A lean-electrolyte full cell using only 10 µL mAh-1 electrolyte is also demonstrated with an elongated lifespan of 100 cycles, five times longer than bare Zn anodes. The cell offers a higher energy density than most existing aqueous batteries. This study presents a proof-of-concept design for low-electrolyte, high-energy-density batteries by modulating coordination interphases on Zn anodes.

Understanding the Degradation Mechanisms of Conducting Polymer Supercapacitors.

Conducting polymers like polyaniline (PANI) are promising pseudocapacitive electrode materials, yet experience instability in cycling performance. Since polymers often degrade into oligomers, short chain length anilines have been developed to improve the cycling stability of PANI-based supercapacitors. However, the capacitance degradation mechanisms of aniline oligomer-based materials have not been systematically investigated and are little understood. Herein, two composite electrodes based on aniline trimers (AT) and carbon nanotubes (CNTs) are studied as model systems and evaluated at both pre-cycling and post-cycling states through physicochemical and electrochemical characterizations. The favorable effect of covalent bonding between AT and CNTs is confirmed to enhance cycling stability by preventing the detachment of aniline trimer and preserving the electrode microstructure throughout the charge/discharge cycling process. In addition, higher porosity has a positive effect on electron/ion transfer and the adaptation to volumetric changes, resulting in higher conductivity and extended cycle life. This work provides insights into the mechanism of enhanced cycling stability of aniline oligomers, indicating design features for aniline oligomer electrode materials to improve their electrochemical performance.

A simple route to functionalized porous carbon foams from carbon nanodots for metal-free pseudocapacitors.

The development of potent pseudocapacitive charge storage materials has emerged as an effective solution for closing the gap between high-energy density batteries and high-power density and long-lasting electrical double-layer capacitors. Sulfonyl compounds are ideal candidates owing to their rapid and reversible redox reactions. However, structural instability and low electrical conductivity hinder their practical application as electrode materials. This work addresses these challenges using a fast and clean laser process to interconnect sulfonated carbon nanodots into functionalized porous carbon frameworks. In this bottom-up approach, the resulting laser-converted three-dimensional (3D) turbostratic carbon foams serve as high-surface-area, conductive scaffolds for redox-active sulfonyl groups. This design enables efficient faradaic processes using pendant sulfonyl groups, leading to a high specific capacitance of 157.6 F g-1 due to the fast reversible redox reactions of sulfonyl moieties. Even at 20 A g-1, the capacitance remained at 78.4% due to the uniform distribution of redox-active sites on the graphitic domains. Additionally, the 3D-tsSC300 electrode showed remarkable cycling stability of >15 000 cycles. The dominant capacitive processes and kinetics were analysed using extensive electrochemical characterizations. Furthermore, we successfully used 3D-tsSC300 in flexible solid-state supercapacitors, achieving a high specific capacitance of up to 17.4 mF cm-2 and retaining 91.6% of the initial capacitance after 20 000 cycles of charge and discharge coupled with 90° bending tests. Additionally, an as-assembled flexible all-solid-state symmetric supercapacitor exhibits a high energy density of 12.6 mW h cm-3 at a high power density of 766.2 W cm-3, both normalized by the volumes of the full device, which is comparable or better than state-of-the-art commercial pseudocapacitors and hybrid capacitors. The integrated supercapacitor provides a wide potential window of 2.0 V using a serial circuit, showing great promise for metal-free energy storage devices.

Roots Fuel Cell Produces and Stores Clean Energy.

In recent years, extensive scientific efforts have been conducted to develop clean bioenergy technologies. A promising approach that has been under development for more than a hundred years is the microbial fuel cell (MFC) which utilizes exoelectrogenic bacteria as an electron source in a bioelectrochemical cell. The viability of bacteria in soil MFCs can be maintained by integrating plant roots, which release organic materials that feed the bacteria. In this work, we show that rather than organic compounds, roots also release redox species that can produce electricity in a biofuel cell. We first studied the reduction of the electron acceptor Cytochrome C by green onion roots. We integrate green onion roots into a biofuel cell to produce a continuous bias-free electric current for more than 24 h in the dark. This current is enhanced upon irradiation of the onion's leaves with light. We apply cyclic voltammetry and 2D-fluorescence measurements to show that NADH and NADPH act as major electron mediators between the roots and the anode, while their concentrations in the external root matrix are increased upon irradiation of the leaves. Finally, we show that roots can contribute to energy storage by charging a supercapacitor.

Mammalian Fuel Cells Produce Electric Current.

The increasing concern about climate change has led scientists around the world to develop clean energy technologies that may replace the traditional use of fossil fuels. A promising approach is the utilization of unicellular organisms as electron donors in bio-fuel cells. To date, this method has been limited to microorganisms such as bacteria, yeast, and microalgae. In this work, we show for the first time the concept of using mammalian cell cultures and organoids as electron donors in biofuel cells. We apply cyclic voltammetry to show that upon association of ARPE19 cells with the anode, they release reducing molecules to produce electricity. Furthermore, we apply 2D-fluorescence measurements and show that upon illumination, photosensitive stem cell-derived retinal organoids, which consist of rod photoreceptors and interneurons, secrete NADH and NADPH molecules that can donate electrons at the anode to produce photocurrent.

Molecular Engineering of Hierarchical Conducting Polymer Composites for Highly Stable Supercapacitors.

Long cycle life and high energy/power density are imperative to energy storage systems. Polyaniline (PANI) has shown great potential as an electrode material but is limited by poor cycling and rate performance. We present a molecular design approach of binding short-chain aniline trimers (ATs) and carbon nanotubes (CNTs) through the formation of amide covalent linkages enabled by a simple laser scribing technique. The covalently coupled AT/CNT (cc-AT/CNT) composite retains 80% of its original capacitance after 20 000 charge/discharge cycles, which readily outperforms long-chain PANI/CNT composites without covalent connections. The compact AT/CNT heterointerfaces produce fast charge/discharge kinetics and excellent rate capability. The flexible symmetric quasi-solid-state devices can be stably cycled beyond 50 000 cycles, at least 5 times longer than most PANI/CNT-based symmetric supercapacitors reported to date. This molecular design of durable conducting polymer-based electrode materials enabled by laser irradiation presents a feasible approach toward robust advanced energy storage devices.

Graphene's Role in Emerging Trends of Capacitive Energy Storage.

Technological breakthroughs in energy storage are being driven by the development of next-generation supercapacitors with favorable features besides high-power density and cycling stability. In this innovation, graphene and its derived materials play an active role. Here, the research status of graphene supercapacitors is analyzed. Recent progress is outlined in graphene assembly, exfoliation, and processing techniques. In addition, electrochemical and electrical attributes that are increasingly valued in next-generation supercapacitors are highlighted along with a summary of the latest research addressing chemical modification of graphene and its derivatives for future supercapacitors. The challenges and solutions discussed in the review hopefully will shed light on the commercialization of graphene and a broader genre of 2D materials in energy storage applications.

Photoreforming of Lignocellulose into H2 Using Nanoengineered Carbon Nitride under Benign Conditions.

Photoreforming of lignocellulose is a promising approach toward sustainable H2 generation, but this kinetically challenging reaction currently requires UV-absorbing or toxic light absorbers under harsh conditions. Here, we report a cyanamide-functionalized carbon nitride, NCNCNx, which shows enhanced performance upon ultrasonication. This activated NCNCNx allows for the visible-light driven conversion of purified and raw lignocellulose samples into H2 in the presence of various proton reduction cocatalysts. The reported room-temperature photoreforming process operates under benign aqueous conditions (pH ≈ 2-15) without the need for toxic components.

Enzymes as modular catalysts for redox half-reactions in H2-powered chemical synthesis: from biology to technology.

The present study considers the ways in which redox enzyme modules are coupled in living cells for linking reductive and oxidative half-reactions, and then reviews examples in which this concept can be exploited technologically in applications of coupled enzyme pairs. We discuss many examples in which enzymes are interfaced with electronically conductive particles to build up heterogeneous catalytic systems in an approach which could be termed synthetic biochemistry We focus on reactions involving the H+/H2 redox couple catalysed by NiFe hydrogenase moieties in conjunction with other biocatalysed reactions to assemble systems directed towards synthesis of specialised chemicals, chemical building blocks or bio-derived fuel molecules. We review our work in which this approach is applied in designing enzyme-modified particles for H2-driven recycling of the nicotinamide cofactor NADH to provide a clean cofactor source for applications of NADH-dependent enzymes in chemical synthesis, presenting a combination of published and new work on these systems. We also consider related photobiocatalytic approaches for light-driven production of chemicals or H2 as a fuel. We emphasise the techniques available for understanding detailed catalytic properties of the enzymes responsible for individual redox half-reactions, and the importance of a fundamental understanding of the enzyme characteristics in enabling effective applications of redox biocatalysis.