Vertical-Channel Cathode Host Enables Rapid Deposition Kinetics toward High-Areal-Capacity Sodium-Chlorine Batteries.

Rechargeable sodium chloride (Na-Cl2) batteries have emerged as promising alternatives for next-generation energy storage due to their superior energy density and sodium abundance. However, their practical applications are hindered by the sluggish chlorine cathode kinetics related to the aggregation of NaCl and its difficult transformation into Cl2. Herein, the study, for the first time from the perspective of electrode level in Na-Cl2 batteries, proposes a free-standing carbon cathode host with customized vertical channels to facilitate the SOCl2 transport and regulate the NaCl deposition. Accordingly, electrode kinetics are significantly enhanced, and the deposited NaCl is distributed evenly across the whole electrode, avoiding the blockage of pores in the carbon host, and facilitating its oxidation to Cl2. With this low-polarization cathode, the Na-Cl2 batteries can deliver a practically high areal capacity approaching 4 mAh cm-2 and a long cycle life of over 170 cycles. This work demonstrates the significance of pore engineering in electrodes for mediating chlorine conversion kinetics in rechargeable alkali-metal-Cl2 batteries.

Band Structure Engineering of Schiff-Base Microporous Organic Polymers for Enhanced Visible-Light Photocatalytic Performance.

Schiff-base networks (SBNs), as typical examples of nitrogen-doped microporous organic polymers (MOPs), exhibit promising application prospects owing to their stable properties and tunable chemical structures. However, their band structure engineering, which plays a key role in optical properties, remains elusive due to the complicated mechanisms behind energy level adjustment. In this work, a series of SBNs are fabricated by tailoring the ratio of p-phthalaldehyde and o-phthalaldehyde in the Schiff-base chemistry reaction with melamine, resulting in a straightforward as well as continuous tuning of their band gaps ranging from 4.4 to 1.4 eV. Consequently, SBNs can be successfully used as photocatalysts with excellent visible-light photocatalytic activity even under metal-free conditions. Significantly, electronic structures of SBNs are systematically studied by electrochemical and spectroscopic characterizations, demonstrating that the enhanced performance is ascribed to proper band structure and improved charge separation ability. More importantly, in combination with theoretical calculations, the band structure regulation mechanism and band structure-photocatalytic property relationship are deeply disclosed. The results obtained from this study will not only furnish SBN materials with excellent performance for solar energy conversion, but also open up elegant protocols for the molecular engineering of MOPs with desirable band structures.

Halbach array assisted assembly of orderly aligned nickel nanowire networks as transparent conductive films.

The aspect ratio and arrangement of nanowires play an important role in achieving excellent optoelectronic performance for metal nanowire-based transparent conductive films (TCFs). However, limited to the technology and material properties, studies are always focused on only one of the issues. Here, a novel strategy for manipulating the relative aspect ratio and arrangement of nickel nanowires (NiNWs) at nanoscale by Halbach array assisted assembly technology is introduced. Head-to-tail nickel nanowire chains as large as hundreds of micrometers are formed as a result of the dipole-dipole interactions of wire-wire. The arrangement of nickel nanowires can be preciously controlled by layer-by-layer deposition. Notably, the alignment create a significant improvement on the optoelectronic performance of nickel nanowire TCFs. The optimized orderly aligned NiNWs TCFs demonstrate super optoelectronic performance (90 Ω sq-1, 86%) than disordered NiNW TCFs (200 Ω sq-1, 80%). Moreover, NiNW-based TCFs exhibit outstanding long-term oxidation stability at 80 °C over 30 d as well as high-temperature oxidization stability even up to 300 °C, that is the most stable metal nanowire-based TCFs in air as far as we know. The low-cost, good optoelectronic performance and excellent oxidation resistance of aligned NiNWs will make them as attractive alternatives to silver nanowires for TCFs application.

Graphene hybridization for energy storage applications.

Graphene has attracted considerable attention due to its unique two-dimensional structure, high electronic mobility, exceptional thermal conductivity, excellent optical transmittance, good mechanical strength, and ultrahigh surface area. To meet the ever increasing demand for portable electronic products, electric vehicles, smart grids, and renewable energy integrations, hybridizing graphene with various functions and components has been demonstrated to be a versatile and powerful strategy to significantly enhance the performance of various energy storage systems such as lithium-ion batteries, supercapacitors and beyond, because such hybridization can result in synergistic effects that combine the best merits of involved components and confer new functions and properties, thereby improving the charge/discharge efficiencies and capabilities, energy/power densities, and cycle life of these energy storage systems. This review will focus on diverse graphene hybridization principles and strategies for energy storage applications, and the proposed outline is as follows. First, graphene and its fundamental properties, followed by graphene hybrids and related hybridization motivation, are introduced. Second, the developed hybridization formulas of using graphene for lithium-ion batteries are systematically categorized from the viewpoint of material structure design, bulk electrode construction, and material/electrode collaborative engineering; the latest representative progress on anodes and cathodes of lithium-ion batteries will be reviewed following such classifications. Third, similar hybridization formulas for graphene-based supercapacitor electrodes will be summarized and discussed as well. Fourth, the recently emerging hybridization formulas for other graphene-based energy storage devices will be briefed in combination with typical examples. Finally, future prospects and directions on the exploration of graphene hybridization toward the design and construction of viable, high-class, and even newly-featured (e.g., flexible) energy storage materials, electrodes, and systems will be presented.

Scallop-Inspired Shell Engineering of Microparticles for Stable and High Volumetric Capacity Battery Anodes.

Building stable and efficient electron and ion transport pathways are critically important for energy storage electrode materials and systems. Herein, a scallop-inspired shell engineering strategy is proposed and demonstrated to confine high volume change silicon microparticles toward the construction of stable and high volumetric capacity binder-free lithium battery anodes. As for each silicon microparticle, the methodology involves an inner sealed but adaptable overlapped graphene shell, and an outer open hollow shell consisting of interconnected reduced graphene oxide, mimicking the scallop structure. The inner closed shell enables simultaneous stabilization of the interfaces of silicon with both carbon and electrolyte, substantially facilitates efficient and rapid transport of both electrons and lithium ions from/to silicon, the outer open hollow shell creates stable and robust transport paths of both electrons and lithium ions throughout the electrode without any sophisticated additives. The resultant self-supported electrode has achieved stable cycling with rapidly increased coulombic efficiency in the early stage, superior rate capability, and remarkably high volumetric capacity upon a facile pressing process. The rational design and engineering of graphene shells of the silicon microparticles developed can provide guidance for the development of a wide range of other high capacity but large volume change electrochemically active materials.

Nitrogen-Enriched Carbon/CNT Composites Based on Schiff-Base Networks: Ultrahigh N Content and Enhanced Lithium Storage Properties.

To improve the electrochemical performance of carbonaceous anodes for lithium ion batteries (LIBs), the incorporation of both well-defined heteroatom species and the controllable 3D porous networks are urgently required. In this work, a novel N-enriched carbon/carbon nanotube composite (NEC/CNT) through a chemically induced precursor-controlled pyrolysis approach is developed. Instead of conventional N-containing sources or precursors, Schiff-base network (SNW-1) enables the desirable combination of a 3D polymer with intrinsic microporosity and ultrahigh N-content, which can significantly promote the fast transport of both Li+ and electron. Significantly, the strong interaction between carbon skeleton and nitrogen atoms enables the retention of ultrahigh N-content up to 21 wt% in the resultant NEC/CNT, which exhibits a super-high capacity (1050 mAh g-1 ) for 1000 cycles and excellent rate performance (500 mAh g-1 at a current density of 5 A g-1 ) as the anode material for LIBs. The NEC/CNT composite affords a new model system as well as a totally different insight for deeply understanding the relationship between chemical structures and lithium ion storage properties, in which chemistry may play a more important role than previously expected.

High-Performance Silicon Battery Anodes Enabled by Engineering Graphene Assemblies.

We propose a novel material/electrode design formula and develop an engineered self-supporting electrode configuration, namely, silicon nanoparticle impregnated assemblies of templated carbon-bridged oriented graphene. We have demonstrated their use as binder-free lithium-ion battery anodes with exceptional lithium storage performances, simultaneously attaining high gravimetric capacity (1390 mAh g(-1) at 2 A g(-1) with respect to the total electrode weight), high volumetric capacity (1807 mAh cm(-3) that is more than three times that of graphite anodes), remarkable rate capability (900 mAh g(-1) at 8 A g(-1)), excellent cyclic stability (0.025% decay per cycle over 200 cycles), and competing areal capacity (as high as 4 and 6 mAh cm(-2) at 15 and 3 mA cm(-2), respectively). Such combined level of performance is attributed to the templated carbon bridged oriented graphene assemblies involved. This engineered graphene bulk assemblies not only create a robust bicontinuous network for rapid transport of both electrons and lithium ions throughout the electrode even at high material mass loading but also allow achieving a substantially high material tap density (1.3 g cm(-3)). Coupled with a simple and flexible fabrication protocol as well as practically scalable raw materials (e.g., silicon nanoparticles and graphene oxide), the material/electrode design developed would propagate new and viable battery material/electrode design principles and opportunities for energy storage systems with high-energy and high-power characteristics.

Structural evolution of 2D microporous covalent triazine-based framework toward the study of high-performance supercapacitors.

A series of nitrogen-containing micropore-donimated materials, porous triazine-based frameworks (PTFs), are constructed through the structural evolution of a 2D microporous covalent triazine-based framework. The PTFs feature predictable and controllable nitrogen doping and pore structures, which serve as a model-like system to more deeply understand the heteroatom effect and micropore effect in ionic liquid-based supercapacitors. The experimental results reveal that the nitrogen doping can enhance the supercapacitor performance mainly through affecting the relative permittivity of the electrode materials. Although microspores' contribution is not as obvious as the doped nitrogen, the great performances of the micropore-dominated PTF suggest that micropore-dominated materials still have great potential in ionic liquid-based supercapacitors.

Graphenal polymers for energy storage.

A key to improve the electrochemical performance of energy storage systems (e.g., lithium ion batteries and supercapacitors) is to develop advanced electrode materials. In the last few years, although originating from the unique structure and property of graphene, interest has expanded beyond the originally literally defined graphene into versatile integration of numerous intermediate structures lying between graphene and organic polymer, particularly for the development of new electrode materials for energy storage devices. Notably, diverse designations have shaded common characteristics of the molecular configurations of these newly-emerging materials, severely impeding the design, synthesis, tailoring, functionalization, and control of functional electrode materials in a rational and systematical manner. This concept paper highlights all these intermediate materials, specifically comprising graphene subunits intrinsically interconnected by organic linkers or fractions, following a general concept of graphenal polymers. Combined with recent advances made by our group and others, two representative synthesis approaches (bottom-up and top-down) for graphenal polymers are outlined, as well as the structure-property relationships of these graphenal polymers as energy storage electrode materials are discussed.

Crucial role of anions on arrangement of Cu2S nanocrystal superstructures.

Both of the arrays of Cu2S nanowires and the superlattices of Cu2S nanoparticles are obtained by the solventless thermolysis of copper thiolate in the presence of laurate. For the first time, the types of anions in the reaction system, which are generally neglected in previous studies, are found to determine the structure of the final assembly products. Furthermore, experimental results shows in the presence of Cl⁻ ions, Cl⁻ ions participate in the self-assembly process and promote the formation of Cu2S nanowire arrays. Finally, the content of Cl⁻ ions is gradually decreased with assembly reaction proceeding. Therefore, duiring the process, Cl⁻ ions play a role of 'catassembly' in the formation of Cu2S nanocrystal superstructures.

Au@MnO2 core-shell nanomesh electrodes for transparent flexible supercapacitors.

A novel Au@MnO2 supercapacitor is presented. The sophisticated core-shell architecture combining an Au nanomesh core with a MnO2 shell on a flexible polymeric substrate is demonstrated as an electrode for high performance transparent flexible supercapacitors (TFSCs). Due to their unique structure, high areal/gravimetric capacitance and rate capability for TFSCs are achieved.

High volumetric capacity silicon-based lithium battery anodes by nanoscale system engineering.

The nanostructuring of silicon (Si) has recently received great attention, as it holds potential to deal with the dramatic volume change of Si and thus improve lithium storage performance. Unfortunately, such transformative materials design principle has generally been plagued by the relatively low tap density of Si and hence mediocre volumetric capacity (and also volumetric energy density) of the battery. Here, we propose and demonstrate an electrode consisting of a textured silicon@graphitic carbon nanowire array. Such a unique electrode structure is designed based on a nanoscale system engineering strategy. The resultant electrode prototype exhibits unprecedented lithium storage performance, especially in terms of volumetric capacity, without the expense of compromising other components of the battery. The fabrication method is simple and scalable, providing new avenues for the rational engineering of Si-based electrodes simultaneously at the individual materials unit scale and the materials ensemble scale.

Covalently stabilized Pd clusters in microporous polyphenylene: an efficient catalyst for Suzuki reactions under aerobic conditions.

A novel catalyst composed of a microporous polyphenylene network and covalently stabilized Pd clusters (Pd/MPP) for highly efficient Suzuki-Miyaura coupling is synthesized with an in-situ one-pot chemical approach, through the catalytic trimerization of 1,3,5-triethynylbenzene. The unique Pd/MPP cluster exhibits very high catalytic activity for a broad scope of Suzuki-Miyaura reactions with short reaction time, good yield, and high turnover number and turnover frequency values, even in aqueous media under aerobic conditions. The strong covalent interaction between Pd and MPP network prevents the agglomeration or leaching of Pd clusters and enables the catalyst to remain highly active, even after a number of cycles.

Pyrolyzed bacterial cellulose: a versatile support for lithium ion battery anode materials.

A scalable, low-cost and environmentally benign strategy is developed for the facile construction of a unique kind of three-dimensional porous electrode architecture for high-performance lithium ion batteries. The methodology is based on the employment of pyrolyzed bacterial cellulose as a new three-dimensional porous scaffold to support various nanostructured active electrode materials, such as SnO2 and Ge.

Reduced graphene oxide nanoribbon networks: a novel approach towards scalable fabrication of transparent conductive films.

An innovative approach is developed for the high-throughput, large-area, and low-cost fabrication of reduced graphene oxide (RGO) nanoribbon networks by using electrospun polymer-based nanowires as the etching mask. Combined with their tunable, controllable structures and transmittance/conductivity properties, the as-fabricated RGO nanoribbon networks exhibit potential as transparent conductive film electrodes, for example, in electrochromic devices.

Enhanced transparent conductive properties of graphene/carbon nano-composite films.

Transparent conductive graphene/carbon nano-composite films are produced based on graphene oxide (GO) sheets and phenolic resins that are layer-by-layer deposited on a quartz substrate using a spin coating technique. The graphene/carbon nano-composite films with high graphitization degree and high crystallization exhibit exceptionally high electrical conductivity and transparency after thermal reduction. A remarkable sheet resistance of 1.98 komega/square at 81.3% transparency in the wavelength of 550 nm is obtained, which significantly outperforms that (3.29 komega/square at 81.7% transparency) of the film produced from pure GO sheets after thermal reduction.

An orientated mass transfer in Ni-Cu tandem nanofibers for highly selective reduction of CO2 to ethanol.

Electrochemically reducing CO2 to ethanol is attractive but suffers from poor selectivity. Tandem catalysis that integrates the activation of CO2 to an intermediate using one active site and the subsequent formation of hydrocarbons on the other site offers a promising approach, where the control of the intermediate transfer between different catalytic sites is challenging. We propose an internally self-feeding mechanism that relies on the orientation of the mass transfer in a hierarchical structure and demonstrate it using a one-dimensional (1D) tandem core-shell catalyst. Specifically, the carbon-coated Ni-core (Ni/C) catalyzes the transformation of CO2-to-CO, after which the CO intermediates are guided to diffuse to the carbon-coated Cu-shell (Cu/C) and experience the selective reduction to ethanol, realizing the orientated key intermediate transfer. Results show that the Faradaic efficiency for ethanol was 18.2% at -1 V vs. RHE (VRHE) for up to 100 h. The following mechanism study supports the hypothesis that the CO2 reduction on Ni/C generates CO, which is further reduced to ethanol on Cu/C sites. Density functional theory calculations suggest a combined effect of the availability of CO intermediate in Ni/C core and the dimerization of key *CO intermediates, as well as the subsequent proton-electron transfer process on the Cu/C shell.

Controlled Isotropic Canalization of Microsized Silicon Enabling Stable High-Rate and High-Loading Lithium Storage.

Silicon is attractive for lithium-ion batteries and beyond but suffers large volume change upon cycling. Hierarchical tactics show promise yet lack control over the unit construction and arrangement, limiting stability improvement at the practical level. Here, a protocol is developed as controlled isotropic canalization of microsized silicon. Distinct from the existing strategies, it involves isotropic canalization by honeycomb-like radial arrangement of silicon nanosheets, and canal consolidation by controlled dual bonding of silicon with carbon. The proof-of-concept nitrogen-doped carbon dual-bonded silicon honeycomb-like microparticles, specifically with a medium density of CNSi and COSi bonds, exhibit stable cycling impressively at high rates and industrial-scale loadings. Two key issues involve isotropic canalization facilitating ion transport in all directions of individual granules and controlled consolidation conferring selective ion permeation and securing charge transport. The study highlights the configurational isotropy and interfacial bonding density, and provides insight into rational design and manufacture of silicon and others with industry-viable features.

Covalent netting restrains dissolution enabling stable high-loading and high-rate iron difluoride cathodes.

Metal fluoride conversion cathodes are promising for the production of cheap, sustainable, and high-energy lithium-ion batteries. Yet, such systems are plagued by active material dissolution that causes capacity fade and hinders commercialization. Here, a covalent netting strategy is proposed to overcome this hurdle. In a proof-of-concept design, polydopamine derived carbon-mediated covalent binding inhibited the dissolution, while the pyrolyzed bacterial cellulose netting structure furnished fast electronic and ionic transport pathways. We demonstrate high-capacity, high-rate and long-lasting stability attained at practical loading levels. Our investigations suggest that the covalent netting-enabled formation of a robust and efficient blocking layer, highly competent in suppressing the leaching, is key for a stable performance. The successful stabilization of metal difluorides in the absence of electrolyte engineering opens an avenue for their practical deployment in future higher-level but lower-cost batteries, and provides a solution to similar challenges encountered by other dissolving energy electrode materials.

Chemical approaches toward graphene-based nanomaterials and their applications in energy-related areas.

A 'gold rush' has been triggered all over the world for exploiting the possible applications of graphene-based nanomaterials. For this purpose, two important problems have to be solved; one is the preparation of graphene-based nanomaterials with well-defined structures, and the other is the controllable fabrication of these materials into functional devices. This review gives a brief overview of the recent research concerning chemical and thermal approaches toward the production of well-defined graphene-based nanomaterials and their applications in energy-related areas, including solar cells, lithium ion secondary batteries, supercapacitors, and catalysis.