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.

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.

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.

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.

Chemically Induced Compatible Interface in Pyrolyzed Bacterial Cellulose/Graphene Sandwich for Electrochemical Energy Storage.

Herein, a three-step approach toward a multi-layered porous PBC/graphene sandwich has been developed, in which the chemical bonding interactions have been successfully enhanced via esterification between the layers of pyrolyzed bacterial cellulose (PBC) and graphene. Such a chemically induced compatible interface has been demonstrated to contribute significantly to the mass transfer efficiency when the PBC/graphene sandwich is deployed as electrode material for both supercapacitors and lithium-sulfur batteries. The high specific capacitance of the supercapacitors has been increased by three times, to 393 F g-1 at 0.1 A g-1. A high initial discharge specific capacity (~1100 mAhg-1) and high coulombic efficiency (99% after 300 cycles) of the rPG/S-based lithium-sulfur batteries have been achieved.

Layer-by-layer stacked vanadium nitride nanocrystals/N-doped carbon hybrid nanosheets toward high-performance aqueous zinc-ion batteries.

Aqueous zinc ion batteries (AZIBs) hold great potential in large scale, low-cost energy storage. Unfortunately, their development is limited by the poor performing cathode materials due to their unstable structures and low capacities. Hence, we develop novel layer-by-layer stacked vanadium nitride nanocrystals/N-doped carbon hybrid nanosheets (VN/NC) as cathode materials by in situ thermal conversion of pyrolyzing pentyl viologen intercalated V2O5. The combination of a leaf-like morphology, the nano structure of vanadium nitride crystals and the conductive porous nitrogen-doped carbon nanosheets endow the VN/NC cathode with excellent electrochemical performance in AZIBs. Thus, it delivers a high discharge specific capacity of 566 mA h g-1 at a current density of 0.2 A g-1 and a superior rate capability. Most importantly, it exhibits a remarkable cyclic stability with capacity retention of 131 mA h g-1 (85% of the initial capacity) after 1000 cycles at a current density of 10 A g-1. The design of the unique VN/NC hybrid nano sheets offers a pathway towards developing high performance electrode materials for energy storage.

A template oriented one-dimensional Schiff-base polymer: towards flexible nitrogen-enriched carbonaceous electrodes with ultrahigh electrochemical capacity.

Lithium-ion capacitors (LICs) have attracted much attention considering their efficient combination of high energy density and high-power density. However, to meet the increasing requirements of energy storage devices and the flexible portable electronic equipment, it is still challenging to develop flexible LIC anodes with high specific capacity and excellent rate capability. Herein, we propose a delicate bottom-up strategy to integrate unique Schiff-base-type polymers into desirable one-dimensional (1D) polymeric structures. A secondary-polymerization-induced template-oriented synthesis approach realizes the 1D integration of Schiff-base porous organic polymers with appealing characteristics of a high nitrogen-doping level and developed pore channels, and a further thermalization yields flexible nitrogen-enriched carbon nanofibers with high specific capacity and fast ion transport. Remarkably, when used as the flexible anode in LICs, the NPCNF//AC LIC demonstrates a high energy density of 154 W h kg-1 at 500 W kg-1 and a high power density of 12.5 kW kg-1 at 104 W h kg-1. This work may provide a new scenario for synthesizing 1D Schiff-base-type polymer derived nitrogen-enriched carbonaceous materials towards promising free-standing anodes in LICs.

Scalable synthesis of silicon nanoplate-decorated graphite for advanced lithium-ion battery anodes.

A silicon nanoplate-decorated graphite design is developed for lithium battery anodes via a simple ball milling process. The resultant silicon-graphite electrodes show high cycling stability with high capacity, superior rate capability, and excellent electrode stability when compared to their counterparts, attributable to two-dimensional silicon and its area-to-area contact with graphite.

Stable high-capacity and high-rate silicon-based lithium battery anodes upon two-dimensional covalent encapsulation.

Silicon is a promising anode material for lithium-ion and post lithium-ion batteries but suffers from a large volume change upon lithiation and delithiation. The resulting instabilities of bulk and interfacial structures severely hamper performance and obstruct practical use. Stability improvements have been achieved, although at the expense of rate capability. Herein, a protocol is developed which we describe as two-dimensional covalent encapsulation. Two-dimensional, covalently bound silicon-carbon hybrids serve as proof-of-concept of a new material design. Their high reversibility, capacity and rate capability furnish a remarkable level of integrated performances when referred to weight, volume and area. Different from existing strategies, the two-dimensional covalent binding creates a robust and efficient contact between the silicon and electrically conductive media, enabling stable and fast electron, as well as ion, transport from and to silicon. As evidenced by interfacial morphology and chemical composition, this design profoundly changes the interface between silicon and the electrolyte, securing the as-created contact to persist upon cycling. Combined with a simple, facile and scalable manufacturing process, this study opens a new avenue to stabilize silicon without sacrificing other device parameters. The results hold great promise for both further rational improvement and mass production of advanced energy storage materials.

A hierarchical layering design for stable, self-restrained and high volumetric binder-free lithium storage.

A hierarchical layering strategy is developed for silicon anodes. The resultant parallelly oriented graphene-sandwiched layered silicon/graphene hybrid microparticles exhibit stable cycling with high volumetric capacity when being charged and discharged at high rates and commercial loading levels, attributable to the designed architecture.

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.

Ultrafast-Charging Silicon-Based Coral-Like Network Anodes for Lithium-Ion Batteries with High Energy and Power Densities.

Fast charging rate and large energy storage are becoming key elements for the development of next-generation batteries, targeting high-performance electric vehicles. Developing electrodes with high volumetric and gravimetric capacity that could be operated at a high rate is the most challenging part of this process. Using silicon as the anode material, which exhibits the highest theoretical capacity as a lithium-ion battery anode, we report a binder-free electrode that interconnects carbon-sheathed porous silicon nanowires into a coral-like network and shows fast charging performance coupled to high energy and power densities when integrated into a full cell with a high areal capacity loading. The combination of interconnected nanowires, porous structure, and a highly conformal carbon coating in a single system strongly promotes the reaction kinetics of the electrode. This leads to fast-charging capability while maintaining the integrity of the electrode without structural collapse and, thus, stable cycling performance without using binder and conductive additives. Specifically, this anode shows high specific capacities (over 1200 mAh g-1) at an ultrahigh charging rate of 7 C over 500 charge-discharge cycles. When coupled with a commercial LiCoO2 or LiFePO4 cathode in a full cell, it delivers a volumetric energy density of 1621 Wh L-1 with a LiCoO2 cathode and a power density of 7762 W L-1 with a LiFePO4 cathode.

Rational Design of Carbon-Rich Materials for Energy Storage and Conversion.

Carbon-rich materials have drawn tremendous attention toward a wide spectrum of energy applications due to their superior electronic mobility, good mechanical strength, ultrahigh surface area, and more importantly, abundant diversity in structure and components. Herein, rationally designed and bottom-up constructed carbon-rich materials for energy storage and conversion are discussed. The fundamental design principles are itemized for the targeted preparation of carbon-rich materials and the latest remarkable advances are summarized in terms of emerging dimensions including sp2 carbon fragment manipulation, pore structure modulation, topological defect engineering, heteroatom incorporation, and edge chemical regulation. In this respect, the corresponding structure-property relationships of the resultant carbon-rich materials are comprehensively discussed. Finally, critical perspectives on future challenges of carbon-rich materials are presented. The progress highlighted here will provide meaningful guidance on the precise design and targeted synthesis of carbon-rich materials, which are of critical importance for the achievement of performance characteristics highly desirable for urgent energy deployment.

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.

A facile and processable integration strategy towards Schiff-base polymer-derived carbonaceous materials with high lithium storage performance.

Herein, a novel in situ concentrated-solution-induced polymerization strategy is developed towards the integration of Schiff-base networks into graphene foam with processable and moldable characteristics. This bottom-up design process endows the resultant composites with a high nitrogen content (9.6 at%) and abundant porosity and accordingly demonstrates high lithium storage properties.

Light-weight 3D Co-N-doped hollow carbon spheres as efficient electrocatalysts for rechargeable zinc-air batteries.

Rational design of cost-effective, nonprecious metal-based catalysts with a desirable oxygen reduction reaction (ORR) performance by a simple and economical synthesis route is a great challenge for the commercialization of future fuel cell and metal-air batteries. Herein, light-weight 3D Co-N-doped hollow carbon spheres (Co-NHCs) have been fabricated via a facile emulsion approach followed by carbonization. The prepared 0.1-Co-NHCs catalyst with suitable Co doping content exhibits favorable ORR catalytic activity (onset potential of 0.99 V and half-wave potential of 0.81 V vs. RHE), comparable to that of commercial Pt-C (onset potential of 1.02 V and half-wave potential of 0.83 V vs. RHE) and rivals that of Pt-C with better cycling stability. The excellent performance of the catalyst is attributed to the synergetic effect of Co and N doping with a high total ratio of active sites, high surface area and good conductivity of the material. More impressively, the assembled rechargeable zinc-air batteries based on the 0.1-Co-NHCs catalyst outperform those afforded by commercial Pt-C. The progress presented in this reported work is of great importance in the development of outstanding non-noble metal based electrocatalysts for the fuel cell and metal-air battery industry.

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.

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.

A collaborative strategy for stable lithium metal anodes by using three-dimensional nitrogen-doped graphene foams.

A collaborative strategy is developed for constructing stable lithium metal anodes by using self-supporting three-dimensional nitrogen-doped graphene foams as the multifunctional host matrix. The resultant electrode shows impressive electrochemical performances, attributable to the three-dimensional porous architecture and nitrogen-doping nature of such a unique host matrix.