Urchin-Like Mesoporous TiN Hollow Sphere Enabling Promoted Electrochemical Kinetics of Bromine-Based Flow Batteries.

Bromine-based flow batteries (BFB) have always suffered from poor kinetics due to the sluggish Br3 -/Br- redox, hindering their practical applications. Developing cathode materials with high catalytic activity is critical to address this challenge. Herein, the in-depth investigation for the free energy of the bromine redox electrode is conducted initially through DFT calculations, establishing the posterior desorption during oxidation as the rate-determining step. An urchin-like titanium nitride hollow sphere (TNHS) composite is designed and synthesized as the catalyst for bromine redox. The large difference in Br- and Br3 - adsorption capability of TNHS promotes rapid desorption of generated Br3 - during the oxidation process, liberating active sites timely to enable smooth ongoing reactions. Besides, the urchin-like microporous/mesoporous structure of TNHS provides abundant active surface for bromine redox reactions, and ample cavities for the bromine accommodation. The inherently high conductivity of TNHS enables facile electron transfer through multiple channels. Consequently, zinc-bromide flow batteries with TNHS catalyst exhibit significantly enhanced kinetics, stably operating at 80 mA cm-2 with 82.78% energy efficiency. Overall, this study offers a solving strategy and catalyst design approach to the sluggish kinetics that has plagued bromine-based flow batteries.

Tix+ in-situ intercalation and interlayer modification via titanium foil/vanadium ion solution interface of VO2.375 as sulfur-wrapped matrix enabling long-life lithium sulfur battery.

Lithium sulfur battery (LSB) has great potential as a promising next-generation energy storage system owing to ultra-high theoretical specific capacity and energy density. However, the polysulfide shuttle effect and slow redox kinetics are recognized the most stumbling blocks on the way of commercializing LSB. On this account, for the first time, we use Tix+ in-situ intercalation strategy via titanium foil/vanadium ion (V5+) solution interface to modify the layer of vanadium oxide for long cycle LSB. The inserted Tix+ strengthens interlayer interaction and enhances lithium-ion mobility rate. Meanwhile, based on density functional theory (DFT) calculation, the mixed valence of V5+/V4+ in the vanadium oxide structure reduces the stress and strain of lithium-ion intercalation through the interlayer support of titanium ions (Tix+). Also, Tix+ refines the structural stability of the sulfur wrapped composite matrix so as to facilitate the LiPSs transformation, and improve the electrochemical performances. Consequently, the Ti-VO2.375/S cathode delivers a lower capacity decay of 0.037 % per cycle over 1500 cycles with a stable coulombic efficiency around 100 %.

Rational construction of graphitic carbon nitride composited Li-rich Mn-based oxide cathode materials toward high-performance Li-ion battery.

Li-rich Mn-based oxides (LRMOs) are considered as one of the most-promising cathode materials for next generation Li-ion batteries (LIBs) because of their high energy density. Nevertheless, the intrinsic shortcomings, such as the low first coulomb efficiency, severe capacity/voltage fade, and poor rate performance seriously limit its commercial application in the future. In this work, we construct successfully g-C3N4 coating layer to modify Li1.2Mn0.54Ni0.13Co0.13O2 (LMNC) via a facile solution. The g-C3N4 layer can alleviate the side-reaction between electrolyte and LMNC materials, and improve electronic conduction of LMNC. In addition, the g-C3N4 layer can suppress the collapse of structure and improve cyclic stability of LMNC materials. Consequently, g-C3N4 (4 wt%)-coated LMNC sample shows the highest initial coulomb efficiency (78.5%), the highest capacity retention ratio (78.8%) and the slightest voltage decay (0.48 V) after 300 loops. Besides, it also can provide high reversible capacity of about 300 and 93 mAh g-1 at 0.1 and 10C, respectively. This work proposes a novel approach to achieve next-generation high-energy density cathode materials, and g-C3N4 (4 wt%)-coated LMNC shows an enormous potential as the cathode materials for next generation LIBs with excellent performance.

Constructing Phase-Transitional NiSx@Nitrogen-Doped Carbon Cathode Material with High Rate Capability and Cycling Stability for Alkaline Zinc-Based Batteries.

Alkaline zinc-based batteries are becoming promising candidates for green and economical energy-storage systems, thanks to their low cost and high energy density. The exploitation of the stable cathode materials with high rate capability and cycling stability is crucial for their further development. Herein, a series of NiSx coated with nitrogen-doped carbon (denoted as NiSx@NC) compounds (x = 0.5-1.0) are synthesized using the facile single-source precursor method. Benefiting from the unique phase-transitional NiSx@NC with high activity and enhanced conductivity from the well-balanced conductive metal nickel and carbon layer, the alkaline zinc-nickel batteries with a phase-transitional NiSx@NC cathode deliver a high capacity of 148 mA h g-1 at a high current density of 100 mA cm-2 and demonstrate a long lifespan of over 500 cycles with a high capacity retention of 98.8%. This work provides a significant guideline for the structural design and optimization of nickel-based materials in alkaline energy-storage devices.

A TiN Nanorod Array 3D Hierarchical Composite Electrode for Ultrahigh-Power-Density Bromine-Based Flow Batteries.

Bromine-based flow batteries are well suited for stationary energy storage due to attractive features of high energy density and low cost. However, the bromine-based flow battery suffers from low power density and large materials consumption due to the relatively high polarization of the Br2 /Br- couple on the electrodes. Herein, a self-supporting 3D hierarchical composite electrode based on a TiN nanorod array is designed to improve the activity of the Br2 /Br- couple and increase the power density of the bromine-based flow battery. In this design, a carbon felt provides a composite electrode with a 3D electron conductive framework to guarantee high electronic conductivity, while the TiN nanorods possess excellent catalytic activity for the Br2 /Br- electrochemical reaction to reduce the electrochemical polarization. Moreover, the 3D micro-nano hierarchical nanorod-array alignment structure contributes to a high electrolyte penetration and a high ion-transfer rate to reduce diffusion polarization. As a result, a zinc-bromine flow battery with the designed composite electrode can be operated at a current density of up to 160 mA cm-2 , which is the highest current density ever reported. These results exhibit a promising strategy to fabricate electrodes for ultrahigh-power-density bromine-based flow batteries and accelerate the development of bromine-based flow batteries.

A membrane-free interfacial battery with high energy density.

A new concept of the membrane-free interfacial battery based on a biphasic system was proposed for the first time. An aqueous ZnBr2 solution was used as a negative electrolyte, while Br2 in CCl4 served as a positive electrolyte. This interfacial Zn/Br2 battery demonstrated a very impressive performance with a CE of 96% and an EE of 81% at a current density of 15 mA cm-2.

Cage-Like Porous Carbon with Superhigh Activity and Br2 -Complex-Entrapping Capability for Bromine-Based Flow Batteries.

Bromine-based flow batteries receive wide attention in large-scale energy storage because of their attractive features, such as high energy density and low cost. However, the Br2 diffusion and relatively low activity of Br2 /Br- hinder their further application. Herein, a cage-like porous carbon (CPC) with specific pore structure combining superhigh activity and Br2 -complex-entrapping capability is designed and fabricated. According to the results of density functional theory (DFT) calculation, the pore size of the CPC (1.1 nm) is well designed between the size of Br- (4.83 Å), MEP+ (9.25 Å), and Br2 complex (MEPBr3 12.40 Å), wherein Br- is oxidized to Br2 , which forms a Br2 complex with the complexing agent immediately and is then entrapped in the cage via pore size exclusion. In addition, the active sites produced during the carbon dioxide activation process dramatically accelerate the reaction rate of Br2 /Br- . In this way, combining a high Br2 -entrapping-capability and high specific surface areas, the CPC shows very impressive performance. The zinc bromine flow battery assembled with the prepared CPC shows a Coulombic efficiency of 98% and an energy efficiency of 81% at the current density of 80 mA cm-2 , which are among the highest values ever reported.

Nitrogen enriched mesoporous carbon as a high capacity cathode in lithium-oxygen batteries.

Nitrogen enriched mesoporous carbon (N-MCS) with extremely high mesopore volume and nitrogen content is prepared through a one-step hard template method. The N-MCS cathode shows excellent discharge performance in lithium-oxygen batteries. The pore space is better utilized due to its optimized pore structure and uniformly incorporated N.

A high-energy-density redox flow battery based on zinc/polyhalide chemistry.

Zn and the Art of Battery Development: A zinc/polyhalide redox flow battery employs Br(-) /ClBr(2-) and Zn/Zn(2+) redox couples in its positive and negative half-cells, respectively. The performance of the battery is evaluated by charge-discharge cycling tests and reveals a high energy efficiency of 81%, based on a Coulombic efficiency of 96% and voltage efficiency of 84%. The new battery technology can provide high performance and energy density at an acceptable cost.

Regulating the zinc ion transport kinetics of Mn3O4 through copper doping towards high-capacity aqueous Zn-ion battery.

High working voltage, large theoretical capacity and cheapness render Mn3O4 promising cathode candidate for aqueous zinc ion batteries (AZIBs). Unfortunately, poor electrochemical activity and bad structural stability lead to low capacity and unsatisfactory cycling performance. Herein, Mn3O4 material was fabricated through a facile precipitation reaction and divalent copper ions were introduced into the crystal framework, and ultra-small Cu-doped Mn3O4 nanocrystalline cathode materials with mixed valence states of Mn2+, Mn3+ and Mn4+ were obtained via post-calcination. The presence of Cu acts as structural stabilizer by partial substitution of Mn, as well as enhance the conductivity and reactivity of Mn3O4. Significantly, based on electrochemical investigations and ex-situ XPS characterization, a synergistic effect between copper and manganese was revealed in the Cu-doped Mn3O4, in which divalent Cu2+ can catalyze the transformation of Mn3+ and Mn4+ to divalent Mn2+, accompanied by the translation of Cu2+ to Cu0 and Cu+. Benefitting from the above advantages, the Mn3O4 cathode doped with moderate copper (abbreviated as CMO-2) delivers large discharge capacity of 352.9 mAh g-1 at 100 mA g-1, which is significantly better than Mn3O4 (only 247.8 mAh g-1). In addition, CMO-2 holds 203.3 mAh g-1 discharge capacity after 1000 cycles at 1 A g-1 with 98.6 % retention, and after 1000 cycles at 5 A g-1, it still performs decent discharge capacity of 104.2 mAh g-1. This work provides new ideas and approaches for constructing manganese-based AZIBs with long lifespan and high capacity.