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.

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.

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.

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.

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.

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).

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.

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.

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.

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.

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction.

Iron phthalocyanine (FePc) is a promising non-precious catalyst for the oxygen reduction reaction (ORR). Unfortunately, FePc with plane-symmetric FeN4 site usually exhibits an unsatisfactory ORR activity due to its poor O2 adsorption and activation. Here, we report an axial Fe-O coordination induced electronic localization strategy to improve its O2 adsorption, activation and thus the ORR performance. Theoretical calculations indicate that the Fe-O coordination evokes the electronic localization among the axial direction of O-FeN4 sites to enhance O2 adsorption and activation. To realize this speculation, FePc is coordinated with an oxidized carbon. Synchrotron X-ray absorption and Mössbauer spectra validate Fe-O coordination between FePc and carbon. The obtained catalyst exhibits fast kinetics for O2 adsorption and activation with an ultralow Tafel slope of 27.5 mV dec-1 and a remarkable half-wave potential of 0.90 V. This work offers a new strategy to regulate catalytic sites for better performance.

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.

Versatile Triboiontronic Transistor via Proton Conductor.

Iontronics are effective in modulating electrical properties through the electric double layers (EDLs) assisted with ionic migration/arrangement, which are highly promising for unconventional electronics, ionic sensory devices, and flexible interactive interface. Proton conductors with the smallest and most abundant protons (H+) can realize a faster migration/polarization under electric field to form the EDL with higher capacitance. Here, a versatile triboiontronic MoS2 transistor via proton conductor by sophisticated combination of triboelectric modulation and protons migration has been demonstrated. This device utilizes triboelectric potential originated from mechanical displacement to modulate the electrical properties of transistors via protons migration/accumulation. It shows superior electrical properties, including high current on/off ratio over 106, low cutoff current (∼0.04 pA), and steep switching properties (89 µm/dec). Pioneering noise tests are conducted to the tribotronic devices to exclude the possible noise interference introduced by mechanical displacement. The versatile triboiontronic MoS2 transistor via proton conductor has been utilized for mechanical behavior derived logic devices and an artificial sensory neuron system. This work represents the reliable and effective triboelectric potential modulation on electronic transportation through protonic dielectrics, which is highly desired for theoretical study of tribotronic gating, active mechanosensation, self-powered electronic skin, artificial intelligence, etc.

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.

Ion Gel Capacitively Coupled Tribotronic Gating for Multiparameter Distance Sensing.

Developing sophisticated device architectures is of great significance to go beyond Moore's law with versatility toward human-machine interaction and artificial intelligence. Tribotronics/tribo-iontronics offer a direct way to controlling the transport properties of semiconductor devices by mechanical actions, which fundamentally relies on how to enhance the tribotronic gating effect through device engineering. Here, we propose a universal method to enhance the tribotronic properties through electric double layer (EDL) capacitive coupling. By preparing an ion gel layer on top of tribotronic graphene transistor, we demonstrate a dual-mode field effect transistor (i.e., a tribotronic transistor with capacitively coupled ion gel and an ion-gel-gated graphene transistor with a second tribotronic gate). The resulted tribotronic gating performances are greatly improved by twice for the on-state current and four times for the on/off ratio (the first mode). It can also be utilized as a multiparameter distance sensor with drain current increased by ∼600 µA and threshold voltage shifted by ∼0.8 V under a mechanical displacement of 0.25 mm (the second mode). The proposed methodology of EDL capacitive coupling offers a facile and efficient way to designing more sophisticated tribotronic devices with superior performance and multifunctional sensations.

How does Molybdenum Disulfide Store Charge: A Minireview.

MoS2 has attracted tremendous attention as a promising electrode material for rechargeable alkali metal ion (Li+ , Na+ , K+ ) batteries due to its high capacity and low cost. However, the practical application of MoS2 for energy storage has not been achieved yet, which is restricted by its intrinsic charge-storage behavior. Debates still exist in this field although great efforts have been made to reveal alkali metal ion (Li+ , Na+ , K+ ) storage mechanism of MoS2 . This Minireview aims to provide an analysis and summary of the related phase conversion, structure collapse, and loss of active material in a MoS2 electrode during the intercalation/extraction process of alkali metal ions. Hence, the fundamental understanding about the charge storage in MoS2 is of importance for the rational design of MoS2 electrodes with excellent electrochemical performance.

Defect Engineering on Electrode Materials for Rechargeable Batteries.

The reasonable design of electrode materials for rechargeable batteries plays an important role in promoting the development of renewable energy technology. With the in-depth understanding of the mechanisms underlying electrode reactions and the rapid development of advanced technology, the performance of batteries has significantly been optimized through the introduction of defect engineering on electrode materials. A large number of coordination unsaturated sites can be exposed by defect construction in electrode materials, which play a crucial role in electrochemical reactions. Herein, recent advances regarding defect engineering in electrode materials for rechargeable batteries are systematically summarized, with a special focus on the application of metal-ion batteries, lithium-sulfur batteries, and metal-air batteries. The defects can not only effectively promote ion diffusion and charge transfer but also provide more storage/adsorption/active sites for guest ions and intermediate species, thus improving the performance of batteries. Moreover, the existing challenges and future development prospects are forecast, and the electrode materials are further optimized through defect engineering to promote the development of the battery industry.