MOF-Derived Nitrogen-Doped Porous Carbon Polyhedrons/Carbon Nanotubes Nanocomposite for High-Performance Lithium-Sulfur Batteries.

Nanocomposites that combine porous materials and a continuous conductive skeleton as a sulfur host can improve the performance of lithium-sulfur (Li-S) batteries. Herein, carbon nanotubes (CNTs) anchoring small-size (~40 nm) N-doped porous carbon polyhedrons (S-NCPs/CNTs) are designed and synthesized via annealing the precursor of zeolitic imidazolate framework-8 grown in situ on CNTs (ZIF-8/CNTs). In the nanocomposite, the S-NCPs serve as an efficient host for immobilizing polysulfides through physical adsorption and chemical bonding, while the interleaved CNT networks offer an efficient charge transport environment. Moreover, the S-NCP/CNT composite with great features of a large specific surface area, high pore volume, and short electronic/ion diffusion depth not only demonstrates a high trapping capacity for soluble lithium polysulfides but also offers an efficient charge/mass transport environment, and an effective buffering of volume changes during charge and discharge. As a result, the Li-S batteries based on a S/S-NCP/CNT cathode deliver a high initial capacity of 1213.8 mAh g-1 at a current rate of 0.2 C and a substantial capacity of 1114.2 mAh g-1 after 100 cycles, corresponding to a high-capacity retention of 91.7%. This approach provides a practical research direction for the design of MOF-derived carbon materials in the application of high-performance Li-S batteries.

Recent advances of bifunctional catalysts for zinc air batteries with stability considerations: from selecting materials to reconstruction.

With the growing depletion of traditional fossil energy resources and ongoing enhanced awareness of environmental protection, research on electrochemical energy storage techniques like zinc-air batteries is receiving close attention. A significant amount of work on bifunctional catalysts is devoted to improving OER and ORR reaction performance to pave the way for the commercialization of new batteries. Although most traditional energy storage systems perform very well, their durability in practical applications is receiving less attention, with issues such as carbon corrosion, reconstruction during the OER process, and degradation, which can seriously impact long-term use. To be able to design bifunctional materials in a bottom-up approach, a summary of different kinds of carbon materials and transition metal-based materials will be of assistance in selecting a suitable and highly active catalyst from the extensive existing non-precious materials database. Also, the modulation of current carbon materials, aimed at increasing defects and vacancies in carbon and electron distribution in metal-N-C is introduced to attain improved ORR performance of porous materials with fast mass and air transfer. Finally, the reconstruction of catalysts is introduced. The review concludes with comprehensive recommendations for obtaining high-performance and highly-durable catalysts.

In situ space-confined growth of Co3O4 nanoparticles inside N-doped hollow porous carbon nanospheres as bifunctional oxygen electrocatalysts for high-performance rechargeable zinc-air batteries.

Developing high-performance and low-cost bifunctional oxygen electrocatalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is of great significance for accelerating the commercialization of rechargeable zinc-air batteries (RZABs). Herein, in situ grown Co3O4 nanoparticle-embedded N-doped hollow porous carbon nanospheres (Co3O4@N-HPCNs) are synthesized via template-assisted pyrolysis as efficient bifunctional ORR/OER electrocatalysts. The N-HPCNs efficiently seize and confine Co3O4 nanoparticles to enhance electronic conductivity and structural stability, while the hollow porous architecture offers adequate mass diffusion pathways to improve the accessibility of reactants and electrolytes on active sites. Therefore, the as-obtained Co3O4-10%@N-HPCNs display outstanding activity and stability for the ORR and the OER, even outperforming commercial Pt/C and Ru/C catalysts. Liquid RZABs assembled with Co3O4-10%@N-HPCN cathodes exhibit a large specific capacity of 768.3 mA h g-1Zn, a high peak power density of 145.6 mW cm-2 and a long-term cycling stability for over 1000 h, demonstrating much-enhanced battery performance in comparison with that of Pt/C + Ru/C based RZABs. Also, flexible quasi-solid-state RZABs assembled with Co3O4-10%@N-HPCN cathodes exhibit a considerable power density of 132.0 mW cm-2 and a stable charge-discharge voltage for a long period even upon bending. This work provides a new approach for the development of catalysts with high activity, long-term stability and low cost.

Flexible All-Solid-State Direct Methanol Fuel Cells with High Specific Power Density.

It is vital to create flexible batteries as power sources to suit the needs of flexible electronic devices because they are widely employed in wearable and portable electronics. The direct methanol fuel cell (DMFC) is a desirable alternative portable energy source since it is a clean, safe, and high energy density cell. The traditional DMFC in mechanical assembly and its unbending property, however, prevent it from being employed in flexible electrical devices. In this study, the flexible membrane electrode assembly (MEA) with superior electrical conductivity and nanoscale TiC-modified carbon cloth (TiC/CC) is used as supporting layer. Additionally, solid methanol fuels used in the manufacturing of flexible all-solid-state DMFC have the advantages of being tiny, light, and having high energy density. Furthermore, the DMFC's placement and bending angle have little effect on its performance, suggesting that DMFC is appropriate for flexible portable energy. The flexible all-solid-state DMFC's power density can reach 14.06 mW cm-2 , and after 50 bends at 60°, its voltage loss can be disregarded. The flexible all-solid DMFC has an energy density that is 777.78 Wh Kg-1 higher than flexible lithium-ion batteries, which is advantageous for the commercialization of flexible electronic products.

A sensor of liquid methanol for direct methanol fuel cells.

The methanol sensors are of significance to maintain the efficient and stable operation of direct methanol fuel cells (DMFCs). The issues, including stability, the relationship between temperature, current density and concentration need, however, urgent attention. A novel electrochemical methanol sensor which is based on current output limited by methanol diffusion is developed. The stability of sensors was lifted steeply through introducing a reference electrode, narrowing the methanol flow channel, and adding a water container. The relationship between the temperature, response current and methanol concentration was determined with the help of theoretical derivation and the validity was verified by the fitting result. Other sensors can avail of this relationship to correct the temperature effect. Application test indicated that the sensor may be of great potential for the accurate monitoring of methanol concentration at the levels of DMFCs application.

An Artificial Polyacrylonitrile Coating Layer Confining Zinc Dendrite Growth for Highly Reversible Aqueous Zinc-Based Batteries.

Aqueous rechargeable zinc-metal-based batteries are an attractive alternative to lithium-ion batteries for grid-scale energy-storage systems because of their high specific capacity, low cost, eco-friendliness, and nonflammability. However, uncontrollable zinc dendrite growth limits the cycle life by piercing the separator, resulting in low zinc utilization in both alkaline and mild/neutral electrolytes. Herein, a polyacrylonitrile coating layer on a zinc anode produced by a simple drop coating approach to address the dendrite issue is reported. The coating layer not only improves the hydrophilicity of the zinc anode but also regulates zinc-ion transport, consequently facilitating the uniform deposition of zinc ions to avoid dendrite formation. A symmetrical cell with the polymer-coating-layer-modified Zn anode displays dendrite-free plating/stripping with a long cycle lifespan (>1100 h), much better than that of the bare Zn anode. The modified zinc anode coupled with a Mn-doped V2 O5 cathode forms a stable rechargeable full battery. This method is a facile and feasible way to solve the zinc dendrite problem for rechargeable aqueous zinc-metal batteries, providing a solid basis for application of aqueous rechargeable Zn batteries.

Co3O4@NiCo2O4 double-shelled nanocages with hierarchical hollow structure and oxygen vacancies as efficient bifunctional electrocatalysts for rechargeable Zn-air batteries.

Highly efficient bifunctional oxygen electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucially important for the rechargeable Zn-air battery, a potential power source for applications in electric vehicles and grid-scale stationary storage systems. Herein, Co3O4@NiCo2O4 double-shelled nanocages (Co3O4@NiCo2O4 DSNCs) with hierarchical hollow structure and oxygen vacancies were designed and synthesized via annealing metal-organic frameworks. Co3O4@NiCo2O4 DSNCs with large specific surface area and three-dimensional interconnected mesopores and cavity not only provide more reaction sites, but also offer an efficient transport environment for reactants. Moreover, oxygen vacancies on the surfaces improve the capture of oxygen species to enhance the reactivity of the catalyst. Consequently, Co3O4@NiCo2O4 DSNCs displayed excellent bifunctional electrocatalytic performance, with a positive half-wave potential of 0.81 V (vs. reversible hydrogen electrode, RHE) for ORR (approaching the potential of commercial Pt/C catalyst) and a low potential of 1.65 V at 10 mA cm-2 for OER (exceeding Pt/C). In a practical demonstration, the Zn-air battery using Co3O4@NiCo2O4 DSNCs as the cathode delivered a satisfactory power density of 102.1 mW cm-2, comparable to the Zn-air battery with a Pt/C cathode, and exhibited much longer cycling stability.

Nylon-Based Composite Gel Membrane Fabricated via Sequential Layer-by-Layer Electrospinning for Rechargeable Lithium Batteries with High Performance.

With the raw materials of poly(vinylidene-co-hexafluoropropylene) (P(VDF-HFP)) and polyamide 6 (PA6, nylon 6), a sandwich-structured composite membrane, PA6/P(VDF-HFP)/PA6, is fabricated via sequential layer-by-layer electrospinning. The nylon-based composite exhibits high absorption to organic liquid electrolyte (270 wt%) owing to its high porosity (90.35%), good mechanical property (17.11 MPa), and outstanding shut-down behavior from approximately 145 to 230 °C. Moreover, the dimensional shrink of a wet PA6 porous membrane immersed into liquid electrolyte is cured due to the existence of the P(VDF-HFP) middle layer. After swelling by the LiPF6-based organic liquid electrolyte, the obtained PA6/P(VDF-HFP)/PA6-based gel polymer electrolytes (GPE) shows high ionic conductivity at room temperature (4.2 mS cm-1), a wide electrochemical stable window (4.8 V), and low activation energy for Li+ ion conduction (4.68 kJ mol-1). Benefiting from the precise porosity structure made of the interlaced electrospinning nanofibers and the superior physicochemical properties of the nylon-based composite GPE, the reversible Li+ ion dissolution/deposition behaviors between the GPE and Li anode are successfully realized with the Li/Li symmetrical cells (current density: 1.0 mA cm-2; areal capacity: 1.0 mAh cm-2) proceeding over 400 h at a polarization voltage of no more than 70 mV. Furthermore, the nylon-based composite GPE in assembled Li/LiFePO4 cells displays good electrochemical stability, high discharge capacity, good cycle durability, and high rate capability. This research provides a new strategy to fabricate gel polymer electrolytes via the electrospinning technique for rechargeable lithium batteries with good electrochemical performance, high security, and low cost.

Covalent Bonding of Si Nanoparticles on Graphite Nanosheets as Anodes for Lithium-Ion Batteries Using Diazonium Chemistry.

Silicon/carbon (Si/C) composite has been proven to be an effective method of enhancing the electrochemical performance of Si-based anodes for lithium-ion batteries (LIBs). However, the practical application of Si/C materials in LIBs is difficult because of the weak interaction between Si and C. In this study, we applied two-step diazotization reactions to modify graphite nanosheets (GNs) and Si nanoparticles (Si NPs), yielding a stable Si-Ar-GNs composite. Owing to aryl (Ar) group bonding, Si NPs were dispersed well on the GNs. The as-prepared Si-Ar-GNs composite delivered an initial reversible capacity of 1174.7 mAh·g-1 at a current density of 100 mAh·g-1. Moreover, capacity remained at 727.3 mAh·g-1 after 100 cycles, showing improved cycling performance. This synthesis strategy can be extended to prepare other Si/C anode materials of LIBs.

A Facile, One-Step Synthesis of Silicon/Silicon Carbide/Carbon Nanotube Nanocomposite as a Cycling-Stable Anode for Lithium Ion Batteries.

Silicon/carbon nanotube (Si/CNTs) nanocomposite is a promising anode material for lithium ion batteries (LIBs). Challenges related to the tricky synthesis process, as well as the weak interaction between Si and CNTs, hinder practical applications. To address these issues, a facile, one-step method to synthesize Si/CNTs nanocomposite by using silica (SiO2) as a reactant via a magnesium reduction process was developed. In this synthesis, the heat released enables the as-obtained Si to react with CNTs in the interfacial region to form silicon carbide (SiC). By virtue of the unique structure composed of Si nanoparticles strongly anchored to conductive CNTs network with stable Si-C chemical bonding, the Si/SiC/CNT nanocomposite delivers a stable capacity of ~1100 mAh g-1 and a capacity retention of about 83.8% after 200 cycles at a current density of 100 mA g-1. Our studies may provide a convenient strategy for the preparation of the Si/C anode of LIBs.

A sandwich-like Si/SiC/nanographite sheet as a high performance anode for lithium-ion batteries.

Silicon/carbon (Si/C) nanocomposite anodes have attracted great interest for their use in lithium-ion batteries (LIBs). However, Si nanoparticles are difficult to stabilize on a carbon surface. Herein, we solve this stabilization problem by designing a Si/silicon carbide/nanographite sheet (Si/SiC/NanoG) nanocomposite. The Si/SiC/NanoG nanocomposite is synthesized by the magnesium thermal reduction of a mixture of silica (SiO2) nanoparticles and NanoG at low temperature, which results in a sandwich-like structure in which the middle SiC layer serves as a linker to stabilize the Si nanoparticles on the surface of NanoGs. Electrochemical characterization shows that the Si/SiC/NanoG nanocomposite anode exhibits outstanding electrochemical performance (an initial reversible capacity of 1135.4 mA h g-1 and 80.4% capacity retention after 100 cycles at 100 mA g-1). This high capacity retention is due to the strong connection between Si and NanoG through the interfacial SiC layer, which buffers the volume changes during the Li-Si alloying-dealloying process. This research will contribute to the design of advanced Si/C anode materials of LIBs.

Methods to Improve Lithium Metal Anode for Li-S Batteries.

The lithium-sulfur (Li-S) battery has received a lot of attention because it is characterized by high theoretical energy density (2,600 Wh/kg) and low cost. Though many works on the "shuttle effect" of polysulfide have been investigated, lithium metal anode is a more challenging problem, which leads to a short life, low coulombic efficiency, and safety issues related to dendrites. As a result, the amelioration of lithium metal anode is an important means to improve the performance of lithium sulfur battery. In this paper, improvement methods on lithium metal anode for lithium sulfur batteries, including adding electrolyte additives, using solid, and/or gel polymer electrolyte, modifying separators, applying a protective coating, and providing host materials for lithium deposition, are mainly reviewed. In addition, some challenging problems, and further promising directions are also pointed out for future research and development of lithium metal for Li-S batteries.

Graphene Oxide-Assisted Synthesis of Pt-Co Alloy Nanocrystals with High-Index Facets and Enhanced Electrocatalytic Properties.

Metal nanocrystals (NCs) are grown directly on the surface of reduced graphene oxide (rGO), which can maximize the rGO-NCs contact/interaction to achieve the enhanced catalytic activity. However, it is difficult to control the size and morphology of metal NCs by in situ method due to the effects of functional groups on the surface of GO, and as a result, the metal NCs/rGO hybrids are conventionally synthesized by two-step method. Herein, one-pot synthesis of Pt-Co alloy NCs is demonstrated with concave-polyhedrons and concave-nanocubes bounded by {hkl} and {hk0} high-index facets (HIFs) distributed on rGO. GO can affect the geometry and electronic structure of Pt-Co NCs. Thanks to the synergy of the HIFs and the electronic effect of the intimate contact/interaction between Pt-Co alloy and rGO, these as-prepared Pt-Co NCs/rGO hybrids presents enhanced catalytic properties for the electrooxidation of formic acid, as well as for the oxygen reduction reaction.

Synthesis of Pt-Ni alloy nanocrystals with high-index facets and enhanced electrocatalytic properties.

The shape-controlled synthesis of multicomponent metal nanocrystals (NCs) bounded by high-index facets (HIFs) is of significant importance in the design and synthesis of high-activity catalysts. We report herein the preparation of Pt-Ni alloy NCs by tuning their shape from concave-nanocubic (CNC) to nanocubic and hexoctahedral (HOH). Owing to the synergy of the HIFs and the electronic effect of the Pt-Ni alloy, the as-prepared CNC and HOH Pt-Ni alloy NCs exhibited excellent catalytic properties for the electrooxidation of methanol and formic acid, as well as for the oxygen reduction reaction (ORR).

Electrochemical synthesis of tetrahexahedral rhodium nanocrystals with extraordinarily high surface energy and high electrocatalytic activity.

Noble metal nanocrystals (NCs) enclosed with high-index facets hold a high catalytic activity thanks to the high density of low-coordinated step atoms that they exposed on their surface. Shape-control synthesis of the metal NCs with high-index facets presents a big challenge owing to the high surface energy of the NCs, and the shape control for metal Rh is even more difficult because of its extraordinarily high surface energy in comparison with Pt, Pd, and Au. The successful synthesis is presented of tetrahexahedral Rh NCs (THH Rh NCs) enclosed by {830} high-index facets through the dynamic oxygen adsorption/desorption mediated by square-wave potential. The results demonstrate that the THH Rh NCs exhibit greatly enhanced catalytic activity over commercial Rh black catalyst for the electrooxidation of ethanol and CO.

Direct electrodeposition of tetrahexahedral Pd nanocrystals with high-index facets and high catalytic activity for ethanol electrooxidation.

Tetrahexahedral Pd nanocrystals (THH Pd NCs) with {730} high-index facets were directly produced on a glassy carbon substrate in a dilute PdCl(2) solution by a newly developed programmed electrodeposition method. The THH Pd NCs, thanks to their high density of surface atomic steps, exhibit 4-6 times higher catalytic activity than commercial Pd black catalyst toward ethanol electrooxidation in alkaline solutions. This straightforward method provides a promising route to facile preparation of high-index-faceted metal nanocatalysts with high catalytic activity.