Utilization of 2D materials in aqueous zinc ion batteries for safe energy storage devices.

Aqueous rechargeable battery has been an intense topic of research recently due to the significant safety issues of conventional Li-ion batteries (LIBs). Amongst the various candidates of aqueous batteries, aqueous zinc ion batteries (AZIBs) hold great promise as a next generation safe energy storage device due to its low cost, abundance in nature, low toxicity, environmental friendliness, low redox potential, and high theoretical capacity. Yet, the promise has not been realized due to their limitations, such as lower capacity compared to traditional LIB, dendrite growth, detrimental degradation of electrode materials structure as ions intercalate/de-intercalate, and gas evolution/corrosion at the electrodes, which remains a significant challenge. To address the challenges, various 2D materials with different physiochemical characteristics have been utilized. This review explores fundamental physiochemical characteristics of widely used 2D materials in AZIBs, including graphene, MoS2, MXenes, 2D metal organic framework, 2D covalent organic framework, and 2D transition metal oxides, and how their characteristics have been utilized or modified to address the challenges in AZIBs. The review also provides insights and perspectives on how 2D materials can help to realize the full potential of AZIBs for next-generation safe and reliable energy storage devices.

Pomegranate-Structured Silica/Sulfur Composite Cathodes for High-Performance Lithium-Sulfur Batteries.

Porous materials have many structural advantages for energy storage and conversion devices such as rechargeable batteries, supercapacitors, and fuel cells. When applied as a host material in lithium-sulfur batteries, porous silica materials with a pomegranate-like architecture can not only act as a buffer matrix for accommodating a large volume change of sulfur, but also suppress the polysulfide shuttle effect. The porous silica/sulfur composite cathodes exhibit excellent electrochemical performances including a high specific capacity of 1450 mA h g-1 , a reversible capacity of 82.9 % after 100 cycles at a rate of C/2 (1 C=1672 mA g-1 ) and an extended cyclability over 300 cycles at 1 C-rate. Furthermore, the high polysulfide adsorption property of porous silica has been proven by ex-situ analyses, showing a relationship between the surface area of silica and polysulfide adsorption ability. In particular, the modified porous silica/sulfur composite cathode, which is treated by a deep-lithiation process in the first discharge step, exhibits a highly reversible capacity of 94.5 % at 1C-rate after 300 cycles owing to a formation of lithiated-silica frames and stable solid-electrolyte-interphase layers.

Multifunctional Free-Standing Gel Polymer Electrolyte with Carbon Nanofiber Interlayers for High-Performance Lithium-Sulfur Batteries.

Free-standing trimethylolpropane ethoxylate triacrylate gel polymer electrolyte is synthesized by a chemical cross-linking process and used as an electrolyte and separator membrane in lithium-sulfur batteries. The cross linked gel polymer electrolyte also exhibited a stable geometric size retention of 95 % at the high temperature of 130 °C. The as-prepared gel polymer electrolyte membrane with carbon nanofibers interlayer can effectively prevent polysulfide dissolution and shuttle effect, leading to significantly enhanced electrochemical properties, including high capacity and cycling stability, with an enhanced specific capacity of 790 mA h g-1 after 100 cycles.

Mesoporous Germanium Anode Materials for Lithium-Ion Battery with Exceptional Cycling Stability in Wide Temperature Range.

Porous structured materials have unique architectures and are promising for lithium-ion batteries to enhance performances. In particular, mesoporous materials have many advantages including a high surface area and large void spaces which can increase reactivity and accessibility of lithium ions. This study reports a synthesis of newly developed mesoporous germanium (Ge) particles prepared by a zincothermic reduction at a mild temperature for high performance lithium-ion batteries which can operate in a wide temperature range. The optimized Ge battery anodes with the mesoporous structure exhibit outstanding electrochemical properties in a wide temperature ranging from -20 to 60 °C. Ge anodes exhibit a stable cycling retention at various temperatures (capacity retention of 99% after 100 cycles at 25 °C, 84% after 300 cycles at 60 °C, and 50% after 50 cycles at -20 °C). Furthermore, full cells consisting of the mesoporous Ge anode and an LiFePO4 cathode show an excellent cyclability at -20 and 25 °C. Mesoporous Ge materials synthesized by the zincothermic reduction can be potentially applied as high performance anode materials for practical lithium-ion batteries.

Zinc-Reduced Mesoporous TiOx Li-Ion Battery Anodes with Exceptional Rate Capability and Cycling Stability.

We demonstrate a unique synthetic route for oxygen-deficient mesoporous TiOx by a redox-transmetalation process by using Zn metal as the reducing agent. The as-obtained materials have significantly enhanced electronic conductivity; 20 times higher than that of as-synthesized TiO2 material. Moreover, electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT) measurements are performed to validate the low charge carrier resistance of the oxygen-deficient TiOx . The resulting oxygen-deficient TiOx battery anode exhibits a high reversible capacity (∼180 mA h g-1 at a discharge/charge rate of 1 C/1 C after 400 cycles) and an excellent rate capability (∼90 mA h g-1 even at a rate of 10 C). Also, the full cell, which is coupled with a LiCoO2 cathode material, exhibits an outstanding rate capability (>75 mA h g-1 at a rate of 3.0 C) and maintains a reversible capacity of over 100 mA h g-1 at a discharge/charge of 1 C/1 C for 300 cycles.

Revisiting Surface Modification of Graphite: Dual-Layer Coating for High-Performance Lithium Battery Anode Materials.

Surface modification of electrode active materials has garnered considerable attention as a facile way to meet stringent requirements of advanced lithium-ion batteries. Here, we demonstrated a new coating strategy based on dual layers comprising antimony-doped tin oxide (ATO) nanoparticles and carbon. The ATO nanoparticles are synthesized via a hydrothermal method and act as electronically conductive/electrochemically active materials. The as-synthesized ATO nanoparticles are introduced on natural graphite along with citric acid used as a carbon precursor. After carbonization, the carbon/ATO-decorated natural graphite (c/ATO-NG) is produced. In the (carbon/ATO) dual-layer coating, the ATO nanoparticles coupled with the carbon layer exhibit unprecedented synergistic effects. The resultant c/ATO-NG anode materials display significant improvements in capacity (530 mA h g(-1) ), cycling retention (capacity retention of 98.1 % after 50 cycles at a rate of C/5), and low electrode swelling (volume expansion of 38 % after 100 cycles) which outperform that of typical graphite materials. Furthermore, a full-cell consisting of a c/ATO-NG anode and an LiNi0.5 Mn1.5 O4 cathode presents excellent cycle retention (capacity retention of >80 % after 100 cycles). We envision that the dual-layer coating concept proposed herein opens a new route toward high-performance anode materials for lithium-ion batteries.

Generalized Redox-Responsive Assembly of Carbon-Sheathed Metallic and Semiconducting Nanowire Heterostructures.

One-dimensional metallic/semiconducting materials have demonstrated as building blocks for various potential applications. Here, we report on a unique synthesis technique for redox-responsive assembled carbon-sheathed metal/semiconducting nanowire heterostructures that does not require a metal catalyst. In our approach, germanium nanowires are grown by the reduction of germanium oxide particles and subsequent self-catalytic growth during the thermal decomposition of natural gas, and simultaneously, carbon sheath layers are uniformly coated on the nanowire surface. This process is a simple, reproducible, size-controllable, and cost-effective process whereby most metal oxides can be transformed into metallic/semiconducting nanowires. Furthermore, the germanium nanowires exhibit stable chemical/thermal stability and outstanding electrochemical performance including a capacity retention of ∼96% after 1200 cycles at the 0.5-1C rate as lithium-ion battery anode.

Enhancement of electrochemical properties by polysulfide trapping in a graphene-coated sulfur cathode on patterned current collector.

A sulfur cathode on a honeycomb-shape-patterned Al current collector was prepared and successfully sealed using triple-layered graphene. Graphene layers on the sulfur cathode well confined the dissolved polysulfide in the electrode, leading to significantly enhanced electrochemical properties including cycle retention and Coulombic efficiency.

Synthesis of Ultrathin Si Nanosheets from Natural Clays for Lithium-Ion Battery Anodes.

Two-dimensional Si nanosheets have been studied as a promising candidate for lithium-ion battery anode materials. However, Si nanosheets reported so far showed poor cycling performances and required further improvements. In this work, we utilize inexpensive natural clays for preparing high quality Si nanosheets via a one-step simultaneous molten salt-induced exfoliation and chemical reduction process. This approach produces high purity mesoporous Si nanosheets in high yield. As a control experiment, two-step process (pre-exfoliated silicate sheets and subsequent chemical reduction) cannot sustain their original two-dimensional structure. In contrast, one-step method results in a production of 5 nm-thick highly porous Si nanosheets. Carbon-coated Si nanosheet anodes exhibit a high reversible capacity of 865 mAh g(-1) at 1.0 A g(-1) with an outstanding capacity retention of 92.3% after 500 cycles. It also delivers high rate capability, corresponding to a capacity of 60% at 20 A g(-1) compared to that of 2.0 A g(-1). Furthermore, the Si nanosheet electrodes show volume expansion of only 42% after 200 cycles.

Electrostatic Force Microscopic Characterization of Early Stage Carbon Deposition on Nickel Anodes in Solid Oxide Fuel Cells.

Carbon deposition on nickel anodes degrades the performance of solid oxide fuel cells that utilize hydrocarbon fuels. Nickel anodes with BaO nanoclusters deposited on the surface exhibit improved performance by delaying carbon deposition (i.e., coking). The goal of this research was to visualize early stage deposition of carbon on nickel surface and to identify the role BaO nanoclusters play in coking resistance. Electrostatic force microscopy was employed to spatially map carbon deposition on nickel foils patterned with BaO nanoclusters. Image analysis reveals that upon propane exposure initial carbon deposition occurs on the Ni surface at a distance from the BaO features. With continued exposure, carbon deposits penetrate into the BaO-modified regions. After extended exposure, carbon accumulates on and covers BaO. The morphology and spatial distribution of deposited carbon was found to be sensitive to experimental conditions.

Printable Solid-State Lithium-Ion Batteries: A New Route toward Shape-Conformable Power Sources with Aesthetic Versatility for Flexible Electronics.

Forthcoming flexible/wearable electronic devices with shape diversity and mobile usability garner a great deal of attention as an innovative technology to bring unprecedented changes in our daily lives. From the power source point of view, conventional rechargeable batteries (one representative example is a lithium-ion battery) with fixed shapes and sizes have intrinsic limitations in fulfilling design/performance requirements for the flexible/wearable electronics. Here, as a facile and efficient strategy to address this formidable challenge, we demonstrate a new class of printable solid-state batteries (referred to as "PRISS batteries"). Through simple stencil printing process (followed by ultraviolet (UV) cross-linking), solid-state composite electrolyte (SCE) layer and SCE matrix-embedded electrodes are consecutively printed on arbitrary objects of complex geometries, eventually leading to fully integrated, multilayer-structured PRISS batteries with various form factors far beyond those achievable by conventional battery technologies. Tuning rheological properties of SCE paste and electrode slurry toward thixotropic fluid characteristics, along with well-tailored core elements including UV-cured triacrylate polymer and high boiling point electrolyte, is a key-enabling technology for the realization of PRISS batteries. This process/material uniqueness allows us to remove extra processing steps (related to solvent drying and liquid-electrolyte injection) and also conventional microporous separator membranes, thereupon enabling the seamless integration of shape-conformable PRISS batteries (including letters-shaped ones) into complex-shaped objects. Electrochemical behavior of PRISS batteries is elucidated via an in-depth analysis of cell impedance, which provides a theoretical basis to enable sustainable improvement of cell performance. We envision that PRISS batteries hold great promise as a reliable and scalable platform technology to open a new concept of cell architecture and fabrication route toward flexible power sources with exceptional shape conformability and aesthetic versatility.

A facile route for growth of CNTs on Si@hard carbon for conductive agent incorporating anodes for lithium-ion batteries.

Conductive agent incorporating Si anodes consisting of directly grown carbon nanotubes on hard carbon encapsulating Si nanoparticles were prepared by a one-pot chemical vapour deposition process. Owing to this fabulous structure, Si-based anodes exhibit excellent cycle retention and rate capability with a high-mass-loading of 3.5 mg cm(-2).

Nanotubular structured Si-based multicomponent anodes for high-performance lithium-ion batteries with controllable pore size via coaxial electro-spinning.

We demonstrate a simple but straightforward process for the synthesis of nanotube-type Si-based multicomponents by combining a coaxial electrospinning technique and subsequent metallothermic reduction reaction. Si-based multicomponent anodes consisting of Si, alumina and titanium silicide show several advantages for high-performance lithium-ion batteries. Alumina and titanium silicide, which have high mechanical properties, act as an effective buffer layer for the large volume change of Si, resulting in outstanding volume suppression behavior (volume expansion of only 14%). Moreover, electrically conductive titanium silicide layers located at the inner and outer layers of a Si nanotube exhibit a high initial coulombic efficiency of 88.5% and an extraordinary rate capability. Nanotubular structured Si-based multicomponents with mechanically and electrically improved components can be used as a promising alternative to conventional graphite anode materials. This synthetic route can be extended to other high capacity lithium-ion battery anode materials.

Cost-effective scalable synthesis of mesoporous germanium particles via a redox-transmetalation reaction for high-performance energy storage devices.

Nanostructured germanium is a promising material for high-performance energy storage devices. However, synthesizing it in a cost-effective and simple manner on a large scale remains a significant challenge. Herein, we report a redox-transmetalation reaction-based route for the large-scale synthesis of mesoporous germanium particles from germanium oxide at temperatures of 420-600 °C. We could confirm that a unique redox-transmetalation reaction occurs between Zn(0) and Ge(4+) at approximately 420 °C using temperature-dependent in situ X-ray absorption fine structure analysis. This reaction has several advantages, which include (i) the successful synthesis of germanium particles at a low temperature (∼450 °C), (ii) the accommodation of large volume changes, owing to the mesoporous structure of the germanium particles, and (iii) the ability to synthesize the particles in a cost-effective and scalable manner, as inexpensive metal oxides are used as the starting materials. The optimized mesoporous germanium anode exhibits a reversible capacity of ∼1400 mA h g(-1) after 300 cycles at a rate of 0.5 C (corresponding to the capacity retention of 99.5%), as well as stable cycling in a full cell containing a LiCoO2 cathode with a high energy density (charge capacity = 286.62 mA h cm(-3)).

A high-performance nanoporous Si/Al2O3 foam lithium-ion battery anode fabricated by selective chemical etching of the Al-Si alloy and subsequent thermal oxidation.

Nanostructured micrometer-sized Al-Si particles are synthesized via a facile selective etching process of Al-Si alloy powder. Subsequent thin Al2O3 layers are introduced on the Si foam surface via a selective thermal wet oxidation process of etched Al-Si particles. The resulting Si/Al2O3 foam anodes exhibit outstanding cycling stability (a capacity retention of 78% after 300 cycles at the C/5 rate) and excellent rate capability.

General approach for high-power li-ion batteries: multiscale lithographic patterning of electrodes.

We demonstrate multiscale patterned electrodes that provide surface-area enhancement and strong adhesion between electrode materials and current collector. The combination of multiscale structured current collector and active materials (anodes and cathodes) enables us to make high-performance Li-ion batteries (LIBs). When LiFePO4 (LFP) cathode and Li4 Ti5 O12 (LTO) anode materials are combined with patterned current collectors, their electrochemical performances are significantly improved, including a high rate capability (LiFePO4 : 100 mAh g(-1) , Li4 Ti5 O12 : 60 mAh g(-1) at 100C rate) and highly stable cycling (LiFePO4 : capacity retention of 99.8% after 50 cycles at 10C rate). Moreover, we successfully fabricate full cell system consisting of patterned LFP cathode and patterned LTO anode, exhibiting high-power battery performances [capacity of approximately 70 mAh g(-1) during 1000 cycles at 10C rate (corresponding to charging/discharging time of 6 min)]. We extend this idea to Si anode that exhibits a large volume change during lithiation/delithiation process. The patterned Si electrodes show significantly enhanced electrochemical performances, including a high specific capacity (825 mAh g(-1) ) at high rate of 5C and a stable cycling retention (88% after 100 cycle at a 0.1C rate). This simple strategy can be extended to other cathode and anode materials for practical LIB applications.

Novel design of ultra-fast Si anodes for Li-ion batteries: crystalline Si@amorphous Si encapsulating hard carbon.

Nanocrystalline Si (c-Si) dispersed in amorphous Si (a-Si) encapsulating hard carbon (HC) has been synthesized as an anode material for fast chargeable lithium-ion batteries. The HC derived from natural polysaccharide was coated by a thin a-Si layer through chemical vapour deposition (CVD) using silane (SiH4) as a precursor gas. The HC@c-Si@a-Si anodes showed an excellent cycle retention of 97.8% even after 200 cycles at a 1 C discharge/charge rate. Furthermore, a high capacity retention of ∼54% of its initial reversible capacity at 0.2 C rate was obtained at a high discharge/charge rate of 5 C. Moreover, the LiCoO2/HC@c-Si@a-Si full-cell showed excellent rate capability and very stable long-term cycle. Even at a rate of 10 C discharge/charge, the capacity retention of the LiCoO2/HC@c-Si@a-Si full-cell was 50.8% of its capacity at a rate of 1 C discharge/charge and showed a superior cycle retention of 80% after 160 cycles at a rate of 1 C discharge/charge.

Flexible high-energy Li-ion batteries with fast-charging capability.

With the development of flexible mobile devices, flexible Li-ion batteries have naturally received much attention. Previously, all reported flexible components have had shortcomings related to power and energy performance. In this research, in order to overcome these problems while maintaining the flexibility, honeycomb-patterned Cu and Al materials were used as current collectors to achieve maximum adhesion in the electrodes. In addition, to increase the energy and power multishelled LiNi0.75Co0.11Mn0.14O2 particles consisting of nanoscale V2O5 and LixV2O5 coating layers and a LiδNi0.75-zCo0.11Mn0.14VzO2 doping layer were used as the cathode-anode composite (denoted as PNG-AES) consisting of amorphous Si nanoparticles (<20 nm) loaded on expanded graphite (10 wt %) and natural graphite (85 wt %). Li-ion cells with these three elements (cathode, anode, and current collector) exhibited excellent power and energy performance along with stable cycling stability up to 200 cycles in an in situ bending test.

A simple fabrication of interconnected CuO nanotube electrodes for high-performance lithium-ion batteries.

Staying connected: Robust and interconnected CuO nanotube anodes were fabricated by a thermal oxidation process of spin-coated CuO nanowire networks. The CuO electrodes strongly adhered to the stainless steel foils and exhibited a high specific capacity (ca. 635 mAh g(-1)), a stable cycling (capacity retention of >99 % after 50 cycles), and excellent rate capabilities (315 mAh g(-1) at 20 C rate).

Preparation of silica nanospheres and porous polymer membranes with controlled morphologies via nanophase separation.

We successfully synthesized two different structures, silica nanospheres and porous polymer membranes, via nanophase separation, based on a sol-gel process. Silica sol, which was in situ polymerized from tetraorthosilicate, was used as a precursor. Subsequently, it was mixed with a polymer that was used as a matrix component. It was observed that nanophase separation occurred after the mixing of polymer with silica sol and subsequent evaporation of solvents, resulting in organizing various structures, from random network silica structures to silica spheres. In particular, silica nanospheres were produced by manipulating the mixing ratio of polymer to silica sol. The size of silica beads was gradually changed from micro- to nanoscale, depending on the polymer content. At the same time, porous polymer membranes were generated by removing the silica component with hydrofluoric acid. Furthermore, porous carbon membranes were produced using carbon source polymer through the carbonization process.