A New Anode for Lithium‐Ion Batteries Based on Single‐Walled Carbon Nanotubes and Graphene: Improved Performance through a Binary Network Design

Carbon nanomaterials, especially graphene and carbon nanotubes, are considered to be favorable alternatives to graphite‐based anodes in lithium‐ion batteries, owing to their high specific surface area, electrical conductivity, and excellent mechanical flexibility. However, the limited number of storage sites for lithium ions within the sp²‐carbon hexahedrons leads to the low storage capacity. Thus, rational structure design is essential for the preparation of high‐performance carbon‐based anode materials. Herein, we employed flexible single‐walled carbon nanotubes (SWCNTs) with ultrahigh electrical conductivity as a wrapper for 3D graphene foam (GF) by using a facile dip‐coating process to form a binary network structure. This structure, which offered high electrical conductivity, enlarged the electrode/electrolyte contact area, shortened the electron‐/ion‐transport pathways, and allowed for efficient utilization of the active material, which led to improved electrochemical performance. When used as an anode in lithium‐ion batteries, the SWCNT‐GF electrode delivered a specific capacity of 953 mA h g^?1 at a current density of 0.1 A g^?1 and a high reversible capacity of 606 mA h g^?1 after 1000 cycles, with a capacity retention of 90 % over 1000 cycles at 1 A g^?1 and 189 mA h g^?1 after 2200 cycles at 5 A g^?1.     

Facile Fabrication of Graphene‐Containing Foam as a High‐Performance Anode for Microbial Fuel Cells

Facile fabrication of novel three‐dimensional anode materials to increase the bacterial loading capacity and improve substrate transport in microbial fuel cells (MFCs) is of great interest and importance. Herein, a novel graphene‐containing foam (GCF) was fabricated easily by freeze‐drying and pyrolysis of a graphene oxide–agarose gel. Owing to the involvement of graphene and stainless‐steel mesh in the GCF, the GCF shows high electrical conductivity, enabling the GCF to be a conductive electrode for MFC applications. With the aid of agarose, the GCF electrode possesses a supermacroporous structure with pore sizes ranging from 100–200 μm and a high surface area, which greatly increase the bacterial loading capacity. Cell viability measurements indicate that the GCF possesses excellent biocompatibility. The MFC, equipped with a 0.4 mm‐thick GCF anode, shows a maximum area power density of 786 mW m^?2, which is 4.1 times that of a MFC equipped with a commercial carbon cloth anode. The simple fabrication route in combination with the outstanding electrochemical performance of the GCF indicates a promising anode for MFC applications.     

Nanoporous gold electrode prepared from gold compact disk as the anode for the microbial fuel cell

The electrodes (anode and cathode) have an important role in the efficiency of a microbial fuel cell (MFC), as they can determine the rate of charge transfer in an electrochemical process. In this study, nanoporous gold electrode, prepared from commercially available gold-made compact disk, is utilized as the anode in a two-chamber MFC. The performance of nanoporous gold electrode in the MFC is compared with that of gold film, carbon felt and acid-heat-treated carbon felt electrodes which are usually employed as the anode in the MFCs. Electrochemical surface area of nanoporous gold electrode exhibits a 7.96-fold increase rather than gold film electrode. Scanning electron microscopy analysis also indicates the homogeneous biofilm is formed on the surface of nanoporous gold electrode, while the biofilm formed at the surface of acid-heat-treated carbon felt electrode shows rough structure. Electrochemical studies show although modifications applied on carbon felt electrodes improve its performance, nanoporous gold electrode, due to its structure and better electrochemical properties, acts more efficiently as the MFC’s anode. The maximum power density produced by nanoporous gold anode is 4.71 mW m^?2 at current density of 16.00 mA m^?2, while this value for acid-heat-treated carbon felt anode is 3.551 mW m^?2 at current density of 9.58 mA m^?2.     

Applicability of Alginate Film Entrapped Yeast for Microbial Fuel Cell

New strategies are proposed for modification of the anode of a Microbial Fuel Cell (MFC). Immobilization of yeast cells as electrogenic microorganism in MFC was reported using alginate. Yeast cells entrapment within alginate matrices was done through films deposited at the surface of a carbon felt electrode and the resulting anodes were characterized by chronoamperometry. Yeast entrapped within alginate films on carbon felt oxidized glucose and generates a current by direct and mediated electrons transfer from yeast cells to the carbon electrode. The result substantiated that immobilization of yeast for MFC could be a promising method to product green electricity.

     

Enhanced power production of microbial fuel cells by reducing the oxygen and nitrogen functional groups of carbon cloth anode

The physicochemical properties of anode material are important for the electron transfer of anode bacteria and electricity generation of microbial fuel cells (MFCs). In this work, carbon cloth anode was pretreated with isopropanol, hydrogen peroxide (H₂O₂) and sodium hypochlorite (NaOCl) in order to reduce the anode functional groups. The influence of functional groups on the electrochemical properties of carbon cloth anode and power generation of MFCs was investigated. The anode pretreatments removed the surface sizing layer of carbon cloth and substantially reduced the contents of C‐O and pyridinic/pyrrolic N groups on the anode. Electrochemical impedance spectroscopy and cyclic voltammetry analyses of the biofilm‐matured anodes revealed an enhanced electrochemical electron transfer property because of the anode pretreatments. As compared with the untreated control (612 ± 6 mW m^?2), the maximum power density of an acetate‐fed single‐chamber MFC was increased by 26% (773 ± 5 mW m^?2) with the isopropanol treated anode. Additional treatment with H₂O₂ and NaOCl further increased the maximum power output to 844 ± 5 mW m^?2 and 831 ± 4 mWm^?2. A nearly inverse liner relationship was observed between the contents of C‐O and pyridinic/pyrrolic N groups on anodes and the anodic exchange current density and the power output of MFCs, indicating an adverse effect of these functional groups on the electricity production of anodes. Results from this study will further our understanding on the microbial interaction with carbon‐based electrodes and provide an important guidance for the modification of anode materials for MFCs in future studies. Copyright © 2016 John Wiley & Sons, Ltd.     

Self‐Recovery of Pd Nanoparticles That Were Dispersed over La(Sr)Fe(Mn)O3 for Intelligent Oxide Anodes of Solid‐Oxide Fuel Cells

Self‐recovery is one of the most‐desirable properties for functional materials. Recently, oxide anodes have attracted significant attention as alternative anode materials for solid‐oxide fuel cells (SOFCs) that can overcome reoxidation, deactivation, and coke‐deposition. However, the electrical conductivity and surface activity of the most‐widely used oxide anodes remain unsatisfactory. Herein, we report the synthesis of an “intelligent oxide anode” that exhibits self‐recovery from power‐density degradation in the redox cycle by using a Pd‐doped La(Sr)Fe‐ (Mn)O₃ cell as an oxide anode for the SOFCs. We investigated the anodic performance and oxidation‐tolerance of the cell by using Pd‐doped perovskite as an anode and fairly high maximum power densities of 0.5 and 0.1 W cm^?2 were achieved at 1073 and 873 K, respectively, despite using a 0.3 mm‐thick electrolyte. Long‐term stability was also examined and the power density was recovered upon exposure of the anode to air. This recovery of the power density can be explained by the formation of Pd nanoparticles, which were self‐recovered through reoxidation and reduction. In addition, the self‐recovery of the anode by oxidation was confirmed by XRD and SEM and this process was effective for improving the durability of SOFC systems when they were exposed to severe operating conditions.     

Carbon and Carbon Hybrid Materials as Anodes for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have attracted much attention for application in large‐scale grid energy storage owing to the abundance and low cost of sodium sources. However, low energy density and poor cycling life hinder practical application of SIBs. Recently, substantial efforts have been made to develop electrode materials to push forward large‐scale practical applications. Carbon materials can be directly used as anode materials, and they show excellent sodium storage performance. Additionally, designing and constructing carbon hybrid materials is an effective strategy to obtain high‐performance anodes for SIBs. In this review, we summarize recent research progress on carbon and carbon hybrid materials as anodes for SIBs. Nanostructural design to enhance the sodium storage performance of anode materials is discussed, and we offer some insight into the potential directions of and future high‐performance anode materials for SIBs.     

Interface Heteroatom‐doping: Emerging Solutions to Silicon‐based Anodes

Silicon‐based composites have been recognized as a promising anode material for high‐energy lithium‐ion batteries (LIBs). However, the intrinsically low conductivity and the huge volume expansion during lithiation/delithiation progresses impede its further practical applications. In the past decades, numerous efforts have been made for surface and interface modification of Si‐based anodes. Among these, doping of active materials with heteroatoms is one promising method to endow silicon many unmatched electrochemical properties. In this review, we focus on the effects of heteroatom doping on the interfacial properties of Si‐based anodes, and some typical strategies for the interface doping are highlighted. We aim to give some reference for interfacial doping of Si‐based anodes in LIBs.     

Nanostructured Graphene/TiO2 Hybrids as High‐Performance Anodes for Microbial Fuel Cells

A new nanostructured graphene/TiO₂ (G/TiO₂) hybrid was synthesized by a facile microwave‐assisted solvothermal process in which amorphous TiO₂ was assembled on graphene in situ. The resulting G/TiO₂ hybrids were characterized by XRD, SEM, TEM, Raman spectroscopy, and N₂ adsorption/desorption analysis. The electrochemical properties of the hybrids as anode materials for Shewanella‐inoculated microbial fuel cells (MFCs) were studied for the first time, and they proved to be effective in improving MFC performance. The significantly improved bacterial attachment and extracellular electron‐transfer efficiency could be attributed to the high specific surface area, active groups, large pore volume, and excellent conductivity of the nanostructured G/TiO₂ hybrid, and this suggests that it could be a promising candidate for high‐performance MFCs.     

Synthesis and Electronic Structure of Boron‐Graphdiyne with an sp‐Hybridized Carbon Skeleton and Its Application in Sodium Storage

Boron‐graphdiyne (BGDY), which has a unique π‐conjugated structure comprising an sp‐hybridized carbon skeleton and evenlydistributed boron heteroatoms in a well‐organized 2D molecular plane, is prepared through a bottom‐up synthetic strategy. Excellent conductivity, a relatively low band gap and a packing mode of the planar BGDY are observed. Notably, the unusual bonding environment of the all sp‐carbon framework and the electron‐deficient boron centers generates affinity to metal atoms, and thus provides extra binding sites. Furthermore, the expanded molecule pores of the BGDY molecular plane can also facilitate the transfer of metal ions in the perpendicular direction. The practical effect of the all sp‐carbon structure and boron heteroatoms on the properties of BGDY are demonstrated in its performance as the anode in sodium‐ion batteries.     

A 3D Organically Synthesized Porous Carbon Material for Lithium‐Ion Batteries

We report the first organically synthesized sp–sp³ hybridized porous carbon, OSPC‐1. This new carbon shows electron conductivity, high porosity, the highest uptake of lithium ions of any carbon material to‐date, and the ability to inhibit dangerous lithium dendrite formation. The new carbon exhibits exceptional potential as anode material for lithium‐ion batteries (LIBs) with high capacity, excellent rate capability, long cycle life, and potential for improved safety performance.     

Stabilizing Lithium into Cross‐Stacked Nanotube Sheets with an Ultra‐High Specific Capacity for Lithium Oxygen Batteries

Although lithium–oxygen batteries possess a high theoretical energy density and are considered as promising candidates for next‐generation power systems, the enhancement of safety and cycling efficiency of the lithium anodes while maintaining the high energy storage capability remains difficult. Here, we overcome this challenge by cross‐stacking aligned carbon nanotubes into porous networks for ultrahigh‐capacity lithium anodes to achieve high‐performance lithium–oxygen batteries. The novel anode shows a reversible specific capacity of 3656 mAh g^?1, approaching the theoretical capacity of 3861 mAh g^?1 of pure lithium. When this anode is employed in lithium–oxygen full batteries, the cycling stability is significantly enhanced, owing to the dendrite‐free morphology and stabilized solid–electrolyte interface. This work presents a new pathway to high performance lithium–oxygen batteries towards practical applications by designing cross‐stacked and aligned structures for one‐dimensional conducting nanomaterials.     

Nafion/Titanium Dioxide‐Coated Lithium Anode for Stable Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have shown great potential as high energy‐storage devices. However, the stability of the Li metal anode is still a major concern. This is due to the formation of lithium dendrites and severe side reactions with polysulfide intermediates. We herein develop an anode protection method by coating a Nafion/TiO₂ composite layer on the Li anode to solve these problems. In this architecture, Nafion suppresses the growth of Li dendrites, protects the Li anode, and prevents side reactions between polysulfides and the Li anode. Moreover, doped TiO₂ further improves the ionic conductivity and mechanical properties of the Nafion membrane. Li–S batteries with a Nafion/TiO₂‐coated Li anode exhibit better cycling stability (776 mA h g^?1 after 100 cycles at 0.2 C, 1 C=1672 mA g^?1) and higher rate performance (787 mA h g^?1 at 2 C) than those with a pristine Li anode. This work provides an alternative way to construct stable Li anodes for high‐performance Li–S batteries.     

Engineering the Distribution of Carbon in Silicon Oxide Nanospheres at the Atomic Level for Highly Stable Anodes

The application of high‐performance silicon‐based anodes, which are among the most prominent anode materials, is hampered by their poor conductivity and large volume expansion. Coupling of silicon‐based anodes with carbonaceous materials is a promising approach to address these issues. However, the distribution of carbon in reported hybrids is normally inhomogeneous and above the nanoscale, which leads to decay of coulombic efficiency during deep galvanostatic cycling. Herein, we report a porous silicon‐based nanocomposite anode derived from phenylene‐bridged mesoporous organosilicas (PBMOs) through a facile sol–gel method and subsequent pyrolysis. PBMOs show molecularly organic–inorganic hybrid character, and the resulting hybrid anode can inherit this unique structure, with carbon distributed homogeneously in the Si‐O‐Si framework at the atomic scale. This uniformly dispersed carbon network divides the silicon oxide matrix into numerous sub‐nanodomains with outstanding structural integrity and cycling stability.     

Graphene Oxide/Carbon Nanotube Composite Hydrogels—Versatile Materials for Microbial Fuel Cell Applications

Carbonaceous nanocomposite hydrogels are prepared with an aid of a suspension polymerization method and are used as anodes in microbial fuel cells (MFCs). (Poly N‐Isopropylacrylamide) (PNIPAM) hydrogels filled with electrically conductive carbonaceous nanomaterials exhibit significantly higher MFC efficiencies than the unfilled hydrogel. The observed morphological images clearly show the homogeneous dispersion of carbon nanotubes (CNTs) and graphene oxide (GO) in the PNIPAM matrix. The complex formation of CNTs and GO with NIPAM is evidenced from the structural characterizations. The effectual MFC performances are influenced by combining the materials of interest (GO and CNTs) and are attributed to the high surface area, number of active sites, and improved electron‐transfer processes. The obtained higher MFC efficiencies associated with an excellent durability of the prepared hydrogels open up new possibilities for MFC anode applications.

     

Poly(siloxane imide) Binder for Silicon‐Based Lithium‐Ion Battery Anodes via Rigidness/Softness Coupling

Binders play a crucial role in maintaining mechanical integrity of electrodes in lithium‐ion batteries. However, the conventional binders lack proper elasticity, and they are not suitable for high‐performance silicon anodes featuring huge volume change during cycling. Herein, a poly(siloxane imide) copolymer (PSI) has been designed, synthesized, and utilized as a binder for silicon‐based anodes. A rigidness/softness coupling mechanism is demonstrated by the PSI binder, which can accommodate volume expansion of the silicon anode upon lithiation. The electrochemical performance in terms of cyclic stability and rate capability can be effectively improved with the PSI binder as demonstrated by a silicon nanoparticle anode.     

Slope‐Dominated Carbon Anode with High Specific Capacity and Superior Rate Capability for High Safety Na‐Ion Batteries

The comprehensive performance of carbon anodes for Na‐ion batteries (NIBs) is largely restricted by their inferior rate capability and safety issues. Herein, a slope‐dominated carbon anode is achieved at a low temperature of 800 °C, which delivers a high reversible capacity of 263 mA h g^?1 at 0.15C with an impressive initial Coulombic efficiency (ICE) of 80 %. When paired with the NaNi_1/3Fe_1/3Mn_1/3O₂ cathode, the reversible capacity at 6C is still 75 % of that at 0.15C, and 73 % of the capacity is retained after 1000 cycles at 3C. The enhanced Na storage performance could be attributed to the unique microstructure with randomly oriented short carbon layers and the relatively higher defect concentration. Given its robustness, such a low‐temperature carbonization strategy could also be applicable to other precursors and provide a new opportunity to design slope‐dominated carbon anodes for high safety, low‐cost NIBs with excellent ICE and superior rate capability.     

A Sodiophilic Interphase‐Mediated,Dendrite‐Free Anode with Ultrahigh Specific Capacity for Sodium‐Metal Batteries

Despite efforts to stabilize sodium metal anodes and prevent dendrite formation, achieving long cycle life with high areal capacities remains difficult owing to a combination of complex failure modes that involve retardant uneven sodium nucleation and subsequent dendrite formation. Now, a sodiophilic interphase based on oxygen‐functionalized carbon nanotube networks is presented, which concurrently facilitates a homogeneous sodium nucleation and a dendrite‐free, lateral growth behavior upon recurring sodium plating/stripping processes. This sodiophilic interphase renders sodium anodes with an ultrahigh capacity of 1078 mAh g^?1 (areal capacity of 10 mAh cm^?2), approaching the theoretical capacity of 1166 mAh g^?1 of pure sodium, as well as a long cycle life up to 3000 cycles. Implementation of this anode allows for the construction of a sodium–air battery with largely enhanced cycling performance owing to the oxygen functionalization‐mediated, dendrite‐free sodium morphology.     

Three-Dimensional Carbon Framework Anchored Polyoxometalate as a High-Performance Anode for Lithium-Ion Batteries

Recently, it has become very important to develop cost-effective anode materials for the large-scale use of lithium-ion batteries (LIBs). Polyoxometalates (POMs) have been considered as one of the most promising alternatives for LIB electrodes owing to their reversible multi-electron-transfer capacity. Herein, Keggin-type [PMo₁₂O₄₀]³⁻ (donated as PMo₁₂) clusters are anchored onto a 3D microporous carbon framework derived from ZIF-8 through electrostatic interactions. The PMo₁₂ clusters can be immobilized steadily and uniformly on the carbon framework, which provides enhanced electrical conductivity and high stability. Compared with PMo₁₂ itself, the as-prepared novel 3D Carbon-PMo₁₂ composite displays a significantly improved Li-ion storage performance as an LIB anode, with excellent reversible specific capacity and rate capacity, as well as high cycling performance (discharge capacity of 985 mA h g⁻¹ after 200 cycles), which are superior to other POM-based anode materials reported so far. The high performance of the Carbon-PMo₁₂ composite can be attributed to the 3D conductive network with fast electron transport, high ratio of pseudocapacitive contribution, and evenly distributed PMo₁₂ clusters with reversible 24-electron transfer capacity. This work offers a facile way to explore novel LIB anodes consisting of electroactive molecule clusters.     

Contact optimization in polymer light‐emitting diodes

To fully exploit the properties of light‐emitting polymers (LEPs) in electroluminescent applications, it is of paramount importance to develop efficient electrical contacts. An ideal electrode is highly conductive, stable, provides a low barrier to carrier injection, and does not degrade the LEP upon contact. It is difficult to find a single homogeneous material that satisfies all of these requirements. Hence, contact optimization has often required the development of multilayer structures. In particular, indium tin oxide covered by a film of poly(ethylene‐dioxythiophene):poly(styrene sulfonic acid) {ITO/PEDOT:PSS} has become a favorite combination for the transparent anode, and heterostructures of LiF and CsF with metals (Al and Ca) have proven to be efficient electron‐injecting contacts. Here we review our progress in the understanding of the operation of light‐emitting diodes incorporating such contacts, in particular by gauging the materials' energy‐level lineup via electroabsorption measurements. Among the series of LEDs investigated, using a high‐energy‐gap blue polyfuorene polymer, CsF/Ca/Al and LiF/Ca/Al electrodes lead to the best improvements in electron injection. The most promising performance for applications, where a high luminance (～1600 cd/m² at 5 V) is also accompanied by a high maximum efficiency (～3 lm/W), was obtained with LiF/Ca/Al cathodes and ITO/PEDOT:PSS anodes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2649–2664, 2003