Roll-Pressed Silicon Anodes with High Reversible Volumetric Capacity Achieved by Interfacial Stabilization and Mechanical Strengthening of a Silicon/Graphene Hybrid Assembly.

Application of Si anodes is hindered by severe capacity fading due to pulverization of Si particles during the large volume changes of Si during charge/discharge and repeated formation of the solid-electrolyte interphase. To address these issues, considerable efforts have been devoted to the development of Si composites with conductive carbons (Si/C composites). However, Si/C composites with high C content inevitably show low volumetric capacity because of low electrode density. For practical applications, the volumetric capacity of a Si/C composite electrode is more important than gravimetric capacity, but volumetric capacity in pressed electrodes is rarely reported. Herein, a novel synthesis strategy is demonstrate for a compact Si nanoparticle/graphene microspherical assembly with interfacial stability and mechanical strength achieved by consecutively formed chemical bonds using 3-aminopropyltriethoxysilane and sucrose. The unpressed electrode (density: 0.71 g cm-3 ) shows a reversible specific capacity of 1470 mAh g-1 with a high initial coulombic efficiency of 83.7% at a current density of 1 C-rate. The corresponding pressed electrode (density: 1.32 g cm-3 ) exhibits high reversible volumetric capacity of 1405 mAh cm-3 and gravimetric capacity of 1520 mAh g-1 with a high initial coulombic efficiency of 80.4% and excellent cycling stability of 83% over 100 cycles at 1 C-rate.

In Situ Growth of Novel Graphene Nanostructures in Reduced Graphene Oxide Microspherical Assembly with Restacking-Resistance and Inter-Particle Contacts for Energy Storage Devices.

Graphene is extensively investigated for various energy storage systems. However, the very low density (<0.01 g cm-3 ) of graphene nanosheets has hindered its further applications. To solve this issue, a controlled assembly of 2D graphene building blocks should be developed into graphene microspheres with high packing density, and restacking of graphene should be prevented to ensure an electrochemically accessible surface area during the assembly. Furthermore, graphene microspheres should have multiple 1D external conductive architecture to promote contacts with the neighbors. This study reports in situ growth of novel graphene nanostructures in reduced graphene oxide microspherical assembly (denoted as GT/GnS@rGB) with restacking resistance and interparticle contacts, for electrochemical energy storage. The GT/GnS@rGB showed high gravimetric (231.8 F g-1 ) and volumetric (181.5 F cm-3 ) capacitances at 0.2 A g-1 in organic electrolyte with excellent rate capabilities of 94.3% (@ 0.2 vs 10 Ag-1 ). Furthermore, GT/GnS@rGB exhibited excellent cycling stability (96.1% of the initial capacitance after 100 000 charge/discharge cycles at 2 A g-1 ). As demonstrated in the electrochemical evaluation as electrode materials for electrical double-layer capacitors, unique structural and textural features of the GT/GnS@rGB would be beneficial in the use of graphene assembly for energy storage applications.

Multi-functionalized herringbone carbon nanofiber for anodes of lithium ion batteries.

Herringbone carbon nanofibers (HCNFs) are prepared for use as anode materials in lithium-ion batteries (LIBs). HCNFs are prepared using a Ni-Fe catalyst and subsequently multi-functionalized with oxygen using the Hummers' method, and then with both oxygen and nitrogen-containing 2-ureido-4[1H]pyrimidinone (UHP) moieties, which endow the HCNFs with the ability to form quadruple hydrogen bonds (QHBs). The as-prepared HCNFs are, on average, 13 µm in length and 100 nm in diameter, with a highly graphitic structure. The oxidized HCNFs (Ox-HCNFs) obtained by Hummers' method are partially exfoliated, having double-bladed saw-like structures that extend in the direction of the graphite planes. QHBs are formed between the HCNFs after functionalization with the UHP moieties. The final surface-modified HCNFs (N-Ox-HCNFs) have more electrochemical sites, shorter Li+ diffusion lengths, and additional electron pathways compared with the as-prepared HCNF and Ox-HCNF. The introduction of oxygen- and nitrogen-containing functional groups improves the performance of LIBs: a high charge capacity of 763 mA h g-1 at 0.1 A g-1, excellent rate capability (a capacity of 402 mA h g-1 at 3 A g-1), and near 100% capacity retention after 300 cycles are reported.

Controlling the intercalation chemistry to design high-performance dual-salt hybrid rechargeable batteries.

We have conducted extensive theoretical and experimental investigations to unravel the origin of the electrochemical properties of hybrid Mg(2+)/Li(+) rechargeable batteries at the atomistic and macroscopic levels. By revealing the thermodynamics of Mg(2+) and Li(+) co-insertion into the Mo6S8 cathode host using density functional theory calculations, we show that there is a threshold Li(+) activity for the pristine Mo6S8 cathode to prefer lithiation instead of magnesiation. By precisely controlling the insertion chemistry using a dual-salt electrolyte, we have enabled ultrafast discharge of our battery by achieving 93.6% capacity retention at 20 C and 87.5% at 30 C, respectively, at room temperature.

Electrochemical properties of graphene flakes as an air cathode material for Li-O2 batteries in an ether-based electrolyte.

We employed graphene flakes as an air-cathode material for Li-O2 batteries and investigated their electrochemical properties in the dimethyl ether electrolyte. Graphene flakes were prepared by microwave-assisted reduction of graphene oxide, and their electrochemical properties were compared with those of Ketjen Black and carbon nanotubes. The catalytic effect of the prepared graphene flake-air cathode was demonstrated using cyclic voltammetry and discharge-charge testing performed under a limited discharge capacity. The catalytic effect of graphene flakes was also supported by morphological and spectroscopic analysis of the discharge-charge products formed on the graphene surface. Scanning electron microscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy revealed that Li2O2, Li2O, and Li2CO3 were the main discharge products on all carbon-air cathode surfaces. Raman spectroscopy revealed that LiRCO3 was additionally formed on Ketjen Black and carbon nanotubes during the first discharge; however, its formation was not observed on the graphene flakes. The catalytic effect of the graphene flakes and the absence of LiRCO3 in the discharge product could explain the higher Coulombic efficiency in the discharge-charge tests.

Synthesis and electrochemical properties of Li0.33MnO2 nanorods as positive electrode material for 3 V lithium batteries.

In this study, one-dimensional Li0.33MnO2 nanorods were synthesized by a solid state reaction using gamma-MnO2 as a precursor. Gamma-MnO2 was prepared under different reaction times by a redox process. The HR-TEM results showed that the diameter and length of the Li0.33MnO2 nanorods are 5-20 nm and about 200 nm, respectively. The Li0.33MnO2 nanorods delivered a discharge capacity of 157 mA h g(-1) at 1 C, and retained 97% of their initial capacity over 30 cycles. Good rate performance was also observed, with discharge capacities of 201 and 133 mA h g(-1) at 0.1 C and 2 C, respectively. The morphology of the nanorods could increase their electrochemical properties, resulting in higher capacity and rate performance.

In Situ Synthesis of Amorphous GeSe/CNT Composite via Defective-carbon-mediated Chemical Bonding for Ultrastable Na Ion Storage.

Herein, we report the in-situ synthesis of amorphous GeSe/CNT composite via defective-carbon-mediated chemical bonding for ultrastable Na-ion storage. Structural defects in CNTs play a crucial role in the chemical bonding and bonding strength in GeSe/CNTs composites. Specifically, the bonding strength tends to increase with increasing defect concentrations of CNTs. Remarkably, the strong chemical bonding between GeSe and CNTs significantly weakens Ge-Se bonds and promotes amorphization of GeSe, thus facilitating a reversible conversion reaction and enhancing Na-ion diffusion. Consequently, GeSe/CNTs composite exhibits outstanding cyclability of 87.9% even after 1000 cycles at 1 A g-1 and a high-rate capability of 288.3 mA h g-1 at 10 A g-1 . Our work presents a promising approach for the amorphization of electrode materials enabled by the defective-carbon-mediated strong chemical bonding for Li-, Na-, and K-ion batteries.

Structurally Reinforced Silicon/Graphene Composite for Lithium-Ion Battery Anodes: Carbon Anchor as a Conductive Structural Support.

Herein, a Si/reduced graphene oxide (rGO)/C microsphere composite is reported, wherein sucrose-derived carbon binds Si nanoparticles (NPs) and rGO to act as a carbon anchor and links neighboring rGO sheets to reinforce the composite structure. In this structurally reinforced Si/rGO/C composite, the electron conduction pathways between rGO and Si NPs were maintained even under large volume changes during repeated charge-discharge processes. Consequently, the Si/rGO/C composite anode exhibited an initial discharge capacity of 1209 mAh g-1 and superior cyclability (92 % retention at 100 cycles), initial coulombic efficiency of 80.5 %, and high-rate capability even at a high C rate (6 C). Furthermore, the change in anode thickness after repeated cycling was negligible, confirming the structural stability imparted by the sucrose-derived carbon binder. A full cell assembled with a LiCoO2 cathode and the Si/rGO/C composite anode remained stable over 200 cycles.

Fe3+-Derived Boosted Charge Transfer in an FeSi4P4 Anode for Ultradurable Li-Ion Batteries.

Ion and electron transportation determine the electrochemical performance of anodes in metal-ion batteries. This study demonstrates the advantage of charge transfer over mass transport in ensuring ultrastable electrochemical performance. Additionally, charge transfer governs the quality, composition, and morphology of a solid-electrolyte interphase (SEI) film. We develop FeSi4P4-carbon nanotube (FSPC) and reduced-FeSi4P4-carbon nanotube (R-FSPC) heterostructures. The FSPC contains abundant Fe3+ cations and negligible pore contents, whereas R-FSPC predominantly comprises Fe2+ and an abundance of nanopores and vacancies. The copious amount of Fe3+ ions in FSPC significantly improves charge transfer during Li-ion battery tests and leads to the formation of a thin monotonic SEI film. This prevents the formation of detrimental LiP and crystalline-Li3.75Si phases and the aggregation of discharging/recharging products and guarantees the reformation of FeSi4P4 nanocrystals during delithiation. Thus, FSPC delivers a high initial Coulombic efficiency (>90%), exceptional rate capability (616 mAh g-1 at 15 A g-1), and ultrastable symmetric/asymmetric cycling performance (>1000 cycles at ultrahigh current densities). This study deepens our understanding of the effects of electron transport on regulating the structural and electrochemical properties of electrode materials in high-performance batteries.

Top-Down Syntheses of Nickel-Based Structured Catalysts for Hydrogen Production from Ammonia.

We report the fabrication and catalytic performance evaluation of highly active and stable nickel (Ni)-based structured catalysts for ammonia dehydrogenation with nearly complete conversion using nonprecious metal catalysts. Low-temperature chemical alloying (LTCA) followed by selective aluminum (Al) dealloying was utilized to synthesize foam-type structured catalysts ready for implementation in commercial-scale catalytic reactors. The crystalline phases of Ni-Al alloy (NiAl3, Ni2Al3, or both) in the near-surface layer were controlled by tuning the alloying time. The best-performing catalyst was obtained from a Ni foam substrate with a NiAl3/Ni2Al3 overlayer synthesized by LTCA at 400 °C for 20 h. The developed Ni catalyst exhibited an activity enhancement of 10-fold over the nontreated Ni foam and showed outstanding activities of 15 800 molH2molNi-1h-1 (TOF: 4.39 s-1) and 19 978 molH2molNi-1h-1 (TOF: 5.55 s-1) at 550 and 600 °C, respectively. This performance is unprecedented compared with previously reported Ni-based ammonia cracking catalysts with higher-end performance (TOFs of 0.08-1.45 s-1 at 550 °C). Moreover, this catalyst showed excellent stability for 100 h at 600 °C while discharging an extremely low NH3 concentration of 1034 ppm. The NH3 concentration in the exhaust gas was further reduced to 690 and 271 ppm at 700 and 800 °C, respectively, while no deactivation was observed at these elevated temperatures. Through material characterizations, we clarified that controlling the degree of Al alloying in the outermost layer of Ni is a crucial factor in determining the activity and stability because residual Al possibly modifies the electronic structure of Ni for enhanced activity as well as transforming to acidic alumina for increased intrinsic activity and stability.

Triethoxysilane-derived SiOx-assisted structural reinforcement of Si/carbon nanotube composite for lithium-ion battery.

Herein, triethoxysilane-derived SiOx is used as a robust adhesive anchor to bind Si nanoparticles (NPs) and carbon nanotubes (CNTs) to prepare a structurally reinforced Si/CNT microsphere composite. The chemical reaction between the silanol groups of triethoxysilane with the hydroxyl groups on the Si surface and acid-treated CNTs induce strong chemical bonds between the Si NPs and CNTs and among neighboring CNTs, facilitating electron-conduction pathways and structural integrity of the composite, even under severe stress/strain. Thus, the structurally reinforced Si/CNT/SiOx microsphere composite exhibits superior cyclability: ∼88% of its initial capacity of 1112 mA h g-1 is retained after 100 cycles at 0.5 A g-1. Moreover, the Si/CNT/SiOx composite exhibits a negligible change in electrode thickness after 100 cycles. The stable electrochemical behavior and negligible change in the electrode thickness are attributed to the maintenance of the electron-conduction pathways and structural integrity of the Si/CNT/SiOx composite, enabled by the binding of neighboring CNTs with the SiOx anchor.

Hybrid Thin-Film Encapsulation for All-Solid-State Thin-Film Batteries.

All-solid-state thin-film batteries have been actively investigated as a power source for various microdevices. However, insufficient research has been conducted on thin-film encapsulation, which is an essential element of these batteries as solid electrolytes and Li anodes are vulnerable to moisture in the atmosphere. In this study, a hybrid thin-film encapsulation structure of hybrid SiOy/SiNxOy/a-SiNx:H/Parylene is suggested and investigated. The water-vapor transmission rate of hybrid thin-film encapsulation is estimated to be 4.9 × 10-3 g m-2·day-1, a value that is applicable to batteries as well as flexible solar cells, thin-film transistor liquid-crystal display, and E-papers. As a result of hybrid thin-film encapsulation, it is confirmed that the all-solid-state thin-film batteries are stable even after 100 charge/discharge cycles in the air atmosphere for 30 days and present a Coulombic efficiency of 99.8% even after 100 cycles in the air atmosphere. These results demonstrate that the thin-film encapsulation structure of hybrid SiOy/SiNxOy/a-SiNx:H/Parylene can be employed in thin-film batteries while retaining long-term stability.

Magnéli Phase Titanium Oxide as a Novel Anode Material for Potassium-Ion Batteries.

Recently, K-ion batteries (KIBs) have attracted attention for potential applications in next-generation energy storage devices principally on the account of their abundancy and lower cost. Herein, for the first time, we report an anatase TiO2-derived Magnéli phase Ti6O11 as a novel anode material for KIBs. We incorporate pristine carbon nanotube (CNT) on the TiO2 host materials due to the low electronic conductivity of the host materials. TiO2 transformed to Magnéli phase Ti6O11 after the first insertion/deinsertion of K ions. From the second cycle, Magnéli phase Ti6O11/CNT composite showed reversible charge/discharge profiles with ∼150 mA h g-1 at 0.05 A g-1. Ex situ X-ray diffraction and transmission electron microscopy analyses revealed that the charge storage process of Magnéli phase Ti6O11 proceeded via the conversion reaction during potassium ion insertion/deinsertion. The Magnéli phase Ti6O11/CNT composite electrode showed long-term cycling life over 500 cycles at 200 mA g-1, exhibiting a capacity retention of 76% and a high Coulombic efficiency of 99.9%. These salient results presented here provide a novel understanding of the K-ion storage mechanisms in the extensively investigated oxide-based material for Li-ion batteries and Na-ion batteries, shedding light on the development of promising electrode materials for next-generation batteries.

Exceptionally Reversible Li-/Na-Ion Storage and Ultrastable Solid-Electrolyte Interphase in Layered GeP5 Anode.

In this study, we synthesize two layered and amorphous structures of germanium phosphide (GeP5) and compare their electrochemical performances to better understand the role of layered, crystalline structures and their ability to control large volume expansions. We compare the results obtained with those of previous, conventional viewpoints addressing the effectiveness of amorphous phases in traditional anodes (Si, Ge, and Sn) to hinder electrode pulverization. By means of both comprehensive experimental characterizations and density functional theory calculations, we demonstrate that layered, crystalline GeP5 in a hybrid structure with multiwalled carbon nanotubes exhibits exceptionally good transport of electrons and electrolyte ions and tolerance to extensive volume changes and provides abundant reaction sites relative to an amorphous structure, resulting in a superior solid-electrolyte interphase layer and unprecedented initial Coulombic efficiencies in both Li-ion and Na-ion batteries. Moreover, the hybrid delivers excellent rate-capability (symmetric and asymmetric) performance and remarkable reversible discharge capacities, even at high current rates, realizing ultradurable cycles in both applications. The findings of this investigation are expected to offer insights into the design and application of layered materials in various devices.

Ultrasound assisted synthesis of nano-sized lithium cobalt oxide.

Nano-sized HT-LiCoO(2) powders were prepared by sonochemical synthesis in an aqueous solution of lithium hydroxide containing cobalt hydroxide at approximately 80 degrees C without any further heat treatment at high temperature. The effects of the LiOH concentration, oxidation conditions, ultrasound irradiation time and temperature on the formation of the nano-sized HT-LiCoO(2) phase were investigated. The formation of the HT-LiCoO(2) phase was confirmed by X-ray diffraction and Raman spectroscopy. The TEM images showed the presence of HT-LiCoO(2) aggregates with a mean particle diameter of approximately 20 nm. The reaction mechanism of the ultrasound assisted synthesis of nano-sized LiCoO(2) was proposed on the basis of the XRD, X-ray absorption spectroscopy analysis and TEM observation of the reaction products taken during the course of the synthesis.

Lithium-Sulfur Capacitors.

Although many existing hybrid energy storage systems demonstrate promising electrochemical performances, imbalances between the energies and kinetics of the two electrodes must be resolved to allow their widespread commercialization. As such, the development of a new class of energy storage systems is a particular challenge, since future systems will require a single device to provide both a high gravimetric energy and a high power density. In this context, we herein report the design of novel lithium-sulfur capacitors. The resulting asymmetric systems exhibited energy densities of 23.9-236.4 Wh kg-1 and power densities of 72.2-4097.3 W kg-1, which are the highest reported values for an asymmetric system to date. This approach involved the use of a prelithiated anode and a hybrid cathode material exhibiting anion adsorption-desorption in addition to the electrochemical reduction and oxidation of sulfur at almost identical rates. This novel strategy yielded both high energy and power densities, and therefore establishes a new benchmark for hybrid systems.

Multimodal porous carbon derived from ionic liquids: correlation between pore sizes and ionic clusters.

In this proof of concept study on the synthesis of ionic liquid (IL)-derived multimodal porous carbon using ionic clusters of different sizes as porogens, the carbonization behaviors of binary IL mixtures of 1-ethyl-3-methylimidazolium dicyanamide (EMIM-dca) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-Tf2N) were systematically investigated to demonstrate the formation of multimodal porous carbons with hierarchical structures originating from the ionic cluster porogens. The multimodal porous structures of the resulting IL-derived porous carbons were characterized based on the quenched solid density functional theory, and the role of the ionic clusters as porogens is discussed. From the viewpoint of green and sustainable chemistry, the IL-based synthesis using ionic clusters as porogens is a simple, effective, and sustainable technique for synthesizing multimodal porous carbons with hierarchical structures. To the best of our knowledge, this is the first study demonstrating that a multimodal porous structure of IL-derived porous carbons could be systematically manipulated with the aid of ionic clusters of different sizes as porogens.

A study of the effects of synthesis conditions on Li5FeO4/carbon nanotube composites.

Li5FeO4/carbon nanotube (LFO/CNT) composites composed of sub-micron sized LFO and a nanocarbon with high electrical conductivity were successfully synthesized for the use as lithium ion predoping source in lithium ion cells. The phase of LFO in the composite was found to be very sensitive to the synthesis conditions, such as the heat treatment temperature, type of lithium salt, and physical state of the precursors (powder or pellet), due to the carbothermic reduction of Fe3O4 by CNTs during high temperature solid state reaction. Under optimized synthesis conditions, LFO/CNT composites could be synthesized without the formation of impurities. To the best of our knowledge, this is the first report on the synthesis and characterization of a sub-micron sized LFO/CNT composites.

Organized and highly dispersed growth of MnO2 nano-rods by sonochemical hydrolysis of Mn3acetate.

Highly dispersed and non-agglomerated alpha-MnO(2) nano-needles of dimensions 20-30 nm have been synthesized by the application of ultrasound radiation on the aqueous solution consisting of manganese(3)acetate close to neutral pH followed by mild drying. With a similar reaction system, hot hydrolysis (non-sonochemical process) produced beta-MnO(2) nano-rods of length 100-200 nm but with high degree agglomeration. Sonochemical cavitation phenomenon is suggested to have a pronounced effect for the formation of special phase and morphology. The effect is proved by the difference in the intermediate products which has difference in crystalinity and phase-purity. The intermediate phases are identified to be single-phase gamma-MnOOH for the non-sonochemical reaction and mixture of gamma-MnOOH, alpha-MnO(2) and beta-MnO(2) for the sonochemical products.

Hierarchically structured activated carbon for ultracapacitors.

To resolve the pore-associated bottleneck problem observed in the electrode materials used for ultracapacitors, which inhibits the transport of the electrolyte ions, we designed hierarchically structured activated carbon (HAC) by synthesizing a mesoporous silica template/carbon composite and chemically activating it to simultaneously remove the silica template and increase the pore volume. The resulting HAC had a well-designed, unique porous structure, which allowed for large interfaces for efficient electric double-layer formation. Given the unique characteristics of the HAC, we believe that the developed synthesis strategy provides important insights into the design and fabrication of hierarchical carbon nanostructures. The HAC, which had a specific surface area of 1,957 m(2) g(-1), exhibited an extremely high specific capacitance of 157 F g(-1) (95 F cc(-1)), as well as a high rate capability. This indicated that it had superior energy storage capability and was thus suitable for use in advanced ultracapacitors.