Accelerating CO2 Electroreduction to Multicarbon Products via Synergistic Electric-Thermal Field on Copper Nanoneedles.

Electrochemical CO2 reduction is a promising way to mitigate CO2 emissions and close the anthropogenic carbon cycle. Among products from CO2RR, multicarbon chemicals, such as ethylene and ethanol with high energy density, are more valuable. However, the selectivity and reaction rate of C2 production are unsatisfactory due to the sluggish thermodynamics and kinetics of C-C coupling. The electric field and thermal field have been studied and utilized to promote catalytic reactions, as they can regulate the thermodynamic and kinetic barriers of reactions. Either raising the potential or heating the electrolyte can enhance C-C coupling, but these come at the cost of increasing side reactions, such as the hydrogen evolution reaction. Here, we present a generic strategy to enhance the local electric field and temperature simultaneously and dramatically improve the electric-thermal synergy desired in electrocatalysis. A conformal coating of ∼5 nm of polytetrafluoroethylene significantly improves the catalytic ability of copper nanoneedles (∼7-fold electric field and ∼40 K temperature enhancement at the tips compared with bare copper nanoneedles experimentally), resulting in an improved C2 Faradaic efficiency of over 86% at a partial current density of more than 250 mA cm-2 and a record-high C2 turnover frequency of 11.5 ± 0.3 s-1 Cu site-1. Combined with its low cost and scalability, the electric-thermal strategy for a state-of-the-art catalyst not only offers new insight into improving activity and selectivity of value-added C2 products as we demonstrated but also inspires advances in efficiency and/or selectivity of other valuable electro-/photocatalysis such as hydrogen evolution, nitrogen reduction, and hydrogen peroxide electrosynthesis.

A Ternary Molten Salt Approach for Direct Regeneration of LiNi0.5 Co0.2 Mn0.3 O2 Cathode.

Recycling spent lithium-ion batteries (LIBs) is an urgent task in view of the resource shortage and environmental concerns. Here, a facile ternary molten salt approach is presented for efficiently regenerating the LiNi0.5 Co0.2 Mn0.3 O2 (NCM523) cathode of spent LIBs. Such an approach involves the treatment of spent cathode powder in the ternary molten salt at a moderate temperature (400 °C) and subsequent annealing in oxygen. The Li loss and degraded phases in spent NCM that cause the capacity decay can be fully remedied after the regeneration process. As a result, the regenerated cathode delivers a reversible capacity of 160 mAh g-1 at 0.5 C with retention of 93.7% after 100 cycles and maintains a high capacity of 132 mAh g-1 at a high rate of 5 C. The electrochemical performance of regenerated NCM cathode is compared favorably to the fresh NCM cathode, which demonstrates the feasibility of the molten salt approach to directly regenerate spent NCM cathode.

Highly Stable Vanadium Redox-Flow Battery Assisted by Redox-Mediated Catalysis.

With good operation flexibility and scalability, vanadium redox-flow batteries (VRBs) stand out from various electrochemical energy storage (EES) technologies. However, traditional electrodes in VRBs, such as carbon and graphite felt with low electrochemical activities, impede the interfacial charge transfer processes and generate considerable overpotential loss, which significantly decrease the energy and voltage efficiencies of VRBs. Herein, by using a facile electrodeposition technique, Prussian blue/carbon felt (PB/CF) composite electrodes with high electrochemical activity for VRBs are successfully fabricated. The PB/CF electrode exhibits excellent electrochemical activity toward VO2+ /VO2 + redox couple in VRB with an average cell voltage efficiency (VE) of 90% and an energy efficiency (EE) of 88% at 100 mA cm-2 . In addition, due to the uniformly distributed PB particles that are strongly bound to the surface of carbon fibers in CF, VRBs with the PB/CF electrodes show much better long-term stabilities compared with the pristine CF-based battery due to the redox-mediated catalysis. A VRB stack consisting of three single cells (16 cm2 ) is also constructed to assess the reliability of the redox-mediated PB/CF electrodes for large-scale application. The facile technique for the high-performance electrode with redox-mediated reaction is expected to shed new light on commercial electrode design for VRBs.

Porous Ni-Mo-Co Hydroxide Nanoflakes on Carbon Cloth for Supercapacitor Application.

To broaden the application of electrode materials, this study firstly provided the high-performance carbon cloth supported mesoporous Ni-Mo-Co hydroxide nanoflakes (NMCOH) by a facile and cost effective hydrothermal method. When directly applied as the electrode for supercapacitor, the high specific capacitance of 1388 F·g-1 at 1 A·g-1, and excellent rate capability about 81.5% at 10 A·g-1 in terms of outstanding cycling stability with 83.2% after 1000 cycles can be achieved. The exceptional super capacitive performances suggested this porous NMCOH nanoflake electrode materials will be a great promise for constructing high-performance energy storage devices.

Facile Synthesis of Tremella-Like V2O5 Microspheres and Their Application as Cathode Materials in Lithium Ion Batteries.

Tremella-like V2O5 microspheres were successfully synthesized in this study through a facile hydrothermal method. The microstructures and electrochemical properties were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) measurements and galvanostatic charge-discharge tests. V2O5 microspheres with unique tremella-like structure exhibited good reversible capacity, with an initial discharge capacity of 147 mA·h·g-1 at 1 C rate. Moreover, the capacity retention rate was 91.36% and charge-discharge efficiency was still over 98% after 400 cycles. Such outstanding properties can be ascribed to their unique tremella-like structure.

Facile Preparation of Nb2O5@Carbon Hollow Microspheres as High-Performance Anode Materials for Lithium-Ion Batteries.

Nb2O5@carbon hollow microspheres (Nb2O5@CHMs) have been synthesized through a facile hydrothermal method. Results revealed that numerous urchin-shaped Nb2O5 nanospheres were tightly and uniformly anchored on the surface of carbon hollow microspheres. Nb2O5@CHMs with unique structure exhibited a high initial discharge capacity of 420.32 mA h·g-1 and an impressive reversible capacity of 350.15 mA h·g-1 after 100 cycles at the current density of 40 mA·g-1. The Nb2O5@CHMs is a potential high-performance anode material for lithium ion batteries.

Synthesis of Mesoporous Co3O4/NiCo2O4 Nanorods and Their Electrochemical Study.

Mesoporous Co3O4/NiCo2O4 nanorods were obtained by a hydrothermal reaction with the assistance of Ni foam and subsequent annealing treatment. The characterization of this composition by X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy dispersive spectra and Brunauer-Emmett-Teller analysis revealed that the nanorods consisted of Co3O4 and NiCo2O4 phase, exhibiting high porosity and rich crystal defects. The electrochemical data showed a specific capacitance of 1173 mF cm-2 and 606 mF cm-2 at 2 mV s-1 and 1 mA cm-2, respectively. Its cycling performance was 83.9% at 3 mA cm-2 after 4000 cycles. Furthermore, the asymmetric supercapacitor Co3O4/NiCo2O4//AC delivered an energy density of 11.7 W h kg-1 and power density of 760 W kg-1.

Unleashing the Power and Energy of LiFePO4-Based Redox Flow Lithium Battery with a Bifunctional Redox Mediator.

Redox flow batteries, despite great operation flexibility and scalability for large-scale energy storage, suffer from low energy density and relatively high cost as compared to the state-of-the-art Li-ion batteries. Here we report a redox flow lithium battery, which operates via the redox targeting reactions of LiFePO4 with a bifunctional redox mediator, 2,3,5,6-tetramethyl-p-phenylenediamine, and presents superb energy density as the Li-ion battery and system flexibility as the redox flow battery. The battery has achieved a tank energy density as high as 1023 Wh/L, power density of 61 mW/cm2, and voltage efficiency of 91%. Operando X-ray absorption near-edge structure measurements were conducted to monitor the evolution of LiFePO4, which provides insightful information on the redox targeting process, critical to the device operation and optimization.

Regulating the solvation structure of Zn2+ via glycine enables a long-cycling neutral zinc-ferricyanide flow battery.

Zinc-based flow batteries hold potential promise for extensive energy storage on a large scale owing to their high energy density and low cost. However, their widespread implementation is impeded by challenges associated with zinc (Zn) dendrites and side reactions like the hydrogen evolution reaction on the anode. Theoretical calculations have confirmed that glycine (Gly) has the ability to coordinate with Zn2+, displacing H2O molecules in the solvation shell, thereby restoring the solvation structure of Zn2+ and promoting the release of reactive Zn2+ during plating/stripping processes. As a result, the incorporation of Gly into the anolyte of a neutral zinc-ferricyanide (Zn/Fe) flow battery (ZIFB) effectively inhibits the formation of Zn dendrites and impedes side reactions, leading to highly reversible and stable Zn plating/stripping reactions. A Zn||Zn symmetric flow battery utilizing Gly in the anolyte demonstrated extended cycling durability, lasting over 550 h at a current density of 30 mA cm-2, in contrast to the failure of a Gly-free anolyte system after 150 h. Notably, this approach facilitates a neutral ZIFB achieving an impressive energy efficiency exceeding 70 %, even at a high current density of 70 mA cm-2, with a cycle lifespan exceeding 800 h (33 days) at a current density of 30 mA cm-2. Conversely, the neutral ZIFB lacking Gly showed a significantly shorter cycle life of only 260 h under identical operational conditions (30 mA cm-2). Due to the economic benefits of Gly and the proposed user-friendly route, this strategy demonstrates great potential for promoting the widespread adoption of zinc-based flow batteries with improved performance for practical use.

One-pot synthesis of boron-doped cobalt oxide nanorod coupled with reduced graphene oxide for sodium ion batteries.

Heteroatom doping is one of the feasible strategies to improve electrode efficiency. Meanwhile, graphene helps to optimize structure and improve conductivity of the electrode. Here, we synthesized a composite of boron-doped cobalt oxide nanorods coupled with reduced graphene oxide by a one-step hydrothermal method and investigated its electrochemical performance for sodium ion storage. Because of the activated boron and conductive graphene, the assembled sodium-ion battery shows excellent cycling stability with a high initial reversible capacity of 424.8 mAh g-1, which is maintained as high as 444.2 mAh g-1 after 50 cycles at a current density of 100 mA g-1. The electrodes also exhibit excellent rate performance with 270.5 mAh g-1 at 2000 mA g-1, and retain 96% of the reversible capacity upon recovery from 100 mA g-1. This study shows that boron doping can increase the capacity of cobalt oxides and graphene can stabilize structure and improve conductivity of the active electrode material, which are essential for achieving satisfactory electrochemical performance. Therefore, the doping of boron and introduction of graphene may be one of the promising means to optimize the electrochemical performance of anode materials.

Redox Targeting-based Neutral Aqueous Flow Battery with High Energy Density and Low Cost.

Neutral aqueous flow batteries with common traits of the redox flow batteries, such as the independence of energy and power, scalability and operational flexibility, and additional merits of outstanding safety and low corrosivity show great promise for storing massive electrical energy from solar and wind energy. Particularly, the ferricyanide/ferrocyanide ([Fe(CN)6 ]3-/4- ) couple has been intensively employed as redox mediator to store energy in the catholyte ascribed to its abundance, low corrosivity, remarkable redox reversibility and stability. However, the low energy density arising from poor solubility of [Fe(CN)6 ]3-/4- restricts their commercial applications for energy storage systems. In this study, the practical energy density of a [Fe(CN)6 ]3-/4- -based catholyte is significantly boosted from 10.5 to 92.8 Wh L-1 by combining the counter-ion effect and the single-molecule redox-targeting (SMRT) reactions between [Fe(CN)6 ]3-/4- and Prussian blue (Fe4 [Fe(CN)6 ]3 , PB)/Prussian white (PW). Paired with concentrated K2 S anolyte, we demonstrate a neutral aqueous SMRT-based PB-Fe/S flow battery with ultra-long lifespan over 7000 cycles (4500 h) and ultra-low chemical cost of electrolytes in the cell as 19.26 $ kWh-1 . Remarkably, under the influences of SMRT reactions in the presence of PB granules in the catholyte, the capacity after 7000 cycles of the PB-Fe/S flow battery is 181.8 % of the initial capacity without PB.

Two-Dimensional Materials Applied in Membranes of Redox Flow Battery.

Redox flow batteries (RFBs) are one of the most promising techniques to store and convert green and renewable energy, benefiting from their advantages of high safety, flexible design and long lifespan. Membranes with fast and selective ions transport are required for the advances of RFBs. Remarkably, two-dimensional (2D) materials with high mechanical and chemical stability, strict size exclusion and abundantly modifiable functional groups, have attracted extensive attentions in the applications of energy fields. Herein, the improvements and perspectives of 2D materials working for ionic transportation and sieving in RFBs membranes are presented. The characteristics of various materials and their advantages and disadvantages in the applications of RFBs membranes particularly are focused. This review is expected to provide a guidance for the design of membranes based on 2D materials for RFBs.

A Stable and Energy-Dense Polysulfide/Permanganate Flow Battery.

Redox flow batteries (RFBs) as promising technologies for energy storage have attracted burgeoning efforts and have achieved many advances in the past decades. However, for practical applications, the exploration of high-performance RFB systems is still of significance. In this work, inspired by the high solubility and low cost of both polysulfides and permanganates, the S/Mn RFBs with S42-/S22- and MnO4-/MnO42- as negative and positive redox pairs are demonstrated. Moreover, to solve the poor cycling performance caused by the sluggish kinetics of polysulfide-involved redox reactions and instability of the carbon felt (CF) electrode in the strong oxidative and corrosive catholyte, both the anode and cathode are designed to obtain high performance. Herein, the NiSx/Ni foam exhibiting electrocatalysis activity toward polysulfide ions is prepared and works as the anode while the graphene-modified carbon felt (G/CF) with high stability is fabricated and utilized as the cathode. Additionally, NaMnO4 with a high solubility limit (3.92 M) in the alkaline supporting electrolyte is preferred to KMnO4 as the redox-active molecule in the catholyte. The resulting S/Mn RFB cells show outstanding cell performance, such as high energy density (67.8 Wh L-1), long cycling lifetime with a temporal capacity fade of 0.025% h-1, and low chemical cost of electrolytes (17.31 $ kWh-1). Moreover, a three-cell stack shows good cycling stability over 100 cycles (226.8 h) with high performance, verifying the good scalability of the proposed S/Mn RFB system. Therefore, the present strategy provides a reliable candidate for stable, energy-dense, and cost-effective devices for future energy storage applications.

Experimental and Theoretical Insights into Enhanced Hydrogen Evolution over PtCo Nanoalloys Anchored on a Nitrogen-Doped Carbon Matrix.

The identification of synergistic effect of Pt-based alloys on hydrogen evolution reaction (HER) requires a combination of experimental studies and theoretical calculations. Here, we present the construction of uniform PtCo nanoparticles grown on N-doped carbon frameworks via pyrolyzing Pt and Co ions adsorbed polyaniline, whereby the nanostructure of the nanoalloys can be effectively tuned by controlling the calcination temperature. As-prepared PtCo@NC-900 shows the optimal HER performance in 0.5 M H2SO4, resulting in a high mass activity of 4.31 A mgPt-1 and excellent operation durability, which far exceeds that of commercial 20 wt % Pt/C (0.30 A mgPt-1). Density functional theory calculations further reveal that the improved HER activity on PtCo(111) is originated from the strong electronic interaction between Pt and Co with favorable electron transfer, allowing for a more suitable binding strength for hydrogen (i.e., ΔG*H = -0.164 eV) compared with that of pristine Pt(111) (-0.287 eV).

Random Copolymer Hydrogel as Elastic Binder for the SiOx Microparticle Anode in Lithium-Ion Batteries.

Silicon suboxides (SiOx) have been widely concerned as a practical anode material for the next-generation lithium-ion batteries due to their relatively high theoretical capacity and lower volume change compared to silicon (Si). Nevertheless, traditional binder poly(vinylidene difluoride) (PVDF) still cannot hold the integrity of the SiOx particle due to its weak van der Waals force. Herein, a copolymer binder for SiOx microparticles is synthesized through a facile method of free radical polymerization between acrylamide (AM) and acrylic acid (AA). By adjusting the mass ratio of the AM/AA monomer, the copolymer binder can generate a covalent-noncovalent network with superior elastic properties from the synergistic effect. During electrochemical testing, the SiOx anode with the optimal copolymer binder (AM/AA = 3:1) delivered a reversible capacity of 734 mAh g-1 (two times that of commercial graphite) at 0.5C after 300 cycles. Thus, this work developed a green and effective strategy for synthesizing a water-soluble binder for Si-based anodes.

Hydrophobic Polymeric Additives toward a Long-Term Robust Carbonaceous Mudstone Slope.

Slopes with carbonaceous mudstone (CM) are widely distributed in the southwest of China and have experienced numerous geological disasters in special climate, especially in rainfall conditions. Therefore, novel materials to stabilize CM slopes have attracted increasing interests. However, developing ultra-stable and cost-effective additives for CM slopes is still a great challenge. Herein, a hydrophobic polymeric material (polyvinylidene fluoride, PVDF) is investigated as an additive to enhance the mechanical strength and long-time stability of CM slopes. The PVDF is uniformly dispersed in CM matrix via interfacial interaction. The contact angle of the PVDF-modified carbonaceous mudstone (PVDF-MCM) can reach as high as 103.95°, indicating an excellent hydrophobicity. The unconfined compressive strength (UCS) and tensile strength (TS) of PVDF-MCM have been intensively enhanced to 4.07 MPa and 1.96 MPa, respectively, compared with ~0 MPa of pristine CM. Moreover, the UCS and TS of PVDF-MCM remain at 3.24 MPa and 1.03 MPa even after curing for 28 days in high humidity conditions. Our findings show that the PVDF can improve the hydrophobicity of CM significantly, which leads to super mechanical stability of PVDF-MCM. The excellent performance makes PVDF a promising additive for the development of ultra-stable, long-lifetime and cost-effective carbonaceous mudstone slopes.

A neutral polysulfide/ferricyanide redox flow battery.

Energy storage systems are crucial in the deployment of renewable energies. As one of the most promising solutions, redox flow batteries (RFBs) are still hindered for practical applications by low energy density, high cost, and environmental concerns. To breakthrough the fundamental solubility limit that restricts boosting energy density of the cell, we here demonstrate a new RFB system employing polysulfide and high concentrated ferricyanide (up to 1.6 M) species as reactants. The RFB cell exhibits high cell performances with capacity retention of 96.9% after 1,500 cycles and low reactant cost of $32.47/kWh. Moreover, neutral aqueous electrolytes are environmentally benign and cost-effective. A cell stack is assembled and exhibits low capacity fade rate of 0.021% per cycle over 642 charging-discharging steps (spans 60 days). This neutral polysulfide/ferricyanide RFB technology with high safety, long-duration, low cost, and feasibility of scale-up is an innovative design for storing massive energy.

Organic Electroactive Molecule-Based Electrolytes for Redox Flow Batteries: Status and Challenges of Molecular Design.

This is a critical review of the advances in the molecular design of organic electroactive molecules, which are the key components for redox flow batteries (RFBs). As a large-scale energy storage system with great potential, the redox flow battery has been attracting increasing attention in the last few decades. The redox molecules, which bridge the interconversion between chemical energy and electric energy for RFBs, have generated wide interest in many fields such as energy storage, functional materials, and synthetic chemistry. The most widely used electroactive molecules are inorganic metal ions, most of which are scarce and expensive, hindering the broad deployment of RFBs. Thus, there is an urgent motivation to exploit novel cost-effective electroactive molecules for the commercialization of RFBs. RFBs based on organic electroactive molecules such as quinones and nitroxide radical derivatives have been studied and have been a hot topic of research due to their inherent merits in the last decade. However, few comprehensive summaries regarding the molecular design of organic electroactive molecules have been published. Herein, the latest progress and challenges of organic electroactive molecules in both non-aqueous and aqueous RFBs are reviewed, and future perspectives are put forward for further developments of RFBs as well as other electrochemical energy storage systems.

Enhanced electrochemical behaviors of carbon felt electrode using redox-active electrolyte for all-solid-state supercapacitors.

In recent decades, redox-active electrolytes have been used in energy storage systems due to high specific capacitance originated from the Faraday reaction of electrode/electrolyte surface. Here, we provide an effective strategy that using H2SO4 as electrolyte with VOSO4 as redox additives to improve the electrochemical performances of the carbon felt (CF) electrode. The function of VOSO4 is that it can serve as a redox-active electrolyte to provide additional specific capacitance. The specific capacitance of 3.30 F cm-2 at 1 mV s-1 can be achieved, which is about 100 times of improved specific capacitance higher than that of the CF electrode tested in pure H2SO4. In addition, it also exhibits unexceptionable cycling stability without any specific capacitance loss after 2000 cycles at 5 mA cm-2. What's more, a novel all-solid-state supercapacitor is assembled using CF, gel electrolyte and membrane. The as-fabricated supercapacitor delivers a high specific capacitance of 234 mF cm-2 and fabulous cycle stability after 1200 cycles at the current density of 2 mA cm-2. Interestingly, three charged supercapacitors connected in series can light a red light-emitting diode effectively for about 24 min. Hence, such mixed electrolyte and electrode materials will hold great potential for high performance supercapacitor applications.

A Cost-effective Nafion Composite Membrane as an Effective Vanadium-Ion Barrier for Vanadium Redox Flow Batteries.

Ion exchange membranes play a key role in all vanadium redox flow batteries (VRFBs). The mostly available commercial membrane for VRFBs is Nafion. However, its disadvantages, such as high cost and severe vanadium-ion permeation, become obstacles for large-scale energy storage. It is thus crucial to develop an efficient membrane with low permeability of vanadium ions and low cost to promote commercial applications of VRFBs. In this study, graphene oxide (GO) has been employed as an additive to the Nafion 212 matrix and a composite membrane named rN212/GO obtained. The thickness of rN212/GO has been reduced to only 41 µm (compared with 50 µm Nafion 212), which indicates directly lower cost. Meanwhile, rN212/GO shows lower permeability of vanadium ions and area-specific resistance compared to the Nafion 212 membrane due to the abundant oxygen-containing functional groups of GO additives. The VRFB cells with the rN212/GO membrane show higher Coulombic efficiencies and lower capacity decay than those of VRFB cells with the Nafion 212 membrane. Therefore, the cost-effective rN212/GO composite membrane is a promising alternative to suppress migration of vanadium ions across the membrane to set up VRFB cells with better performances.