Issues and Challenges Facing Flexible Lithium-Ion Batteries for Practical Application.

With the advent of flexible electronics, lithium-ion batteries have become a key component of high performance energy storage systems. Thus, considerable effort is made to keep up with the development of flexible lithium-ion batteries. To date, many researchers have studied newly designed batteries with flexibility, however, there are several significant challenges that need to be overcome, such as degradation of electrodes under external load, poor battery performance, and complicated cell preparation procedures. In addition, an in-depth understanding of the current challenges for flexible batteries is rarely addressed in a systematical and practical way. Herein, recent progress and current issues of flexible lithium-ion batteries in terms of battery materials and cell designs are reviewed. A critical overview of important issues and challenges for the practical application of flexible lithium-ion batteries is also provided. Finally, the strategies are discussed to overcome current limitations of the practical use of flexible lithium-based batteries, providing a direction for future research.

Unveiling the Catalytic Origin of Nanocrystalline Yttrium Ruthenate Pyrochlore as a Bifunctional Electrocatalyst for Zn-Air Batteries.

Zn-air batteries suffer from the slow kinetics of oxygen reduction reaction (ORR) and/or oxygen evolution reaction (OER). Thus, the bifunctional electrocatalysts are required for the practical application of rechargeable Zn-air batteries. In terms of the catalytic activity and structural stability, pyrochlore oxides (A2[B2-xAx]O7-y) have emerged as promising candidates. However, a limited use of A-site cations (e.g., lead or bismuth cations) of reported pyrochlore catalysts have hampered broad understanding of their catalytic effect and structure. More seriously, the catalytic origin of the pyrochlore structure was not clearly revealed yet. Here, we report the new nanocrystalline yttrium ruthenate (Y2[Ru2-xYx]O7-y) with pyrochlore structure. The prepared pyrochlore oxide demonstrates comparable catalytic activities in both ORR and OER, compared to that of previously reported metal oxide-based catalysts such as perovskite oxides. Notably, we first find that the catalytic activity of the Y2[Ru2-xYx]O7-y is associated with the oxidations and corresponding changes of geometric local structures of yttrium and ruthenium ions during electrocatalysis, which were investigated by in situ X-ray absorption spectroscopy (XAS) in real-time. Zn-air batteries using the prepared pyrochlore oxide achieve highly enhanced charge and discharge performance with a stable potential retention for 200 cycles.

Ultrathin Al2O3 interface achieving an 11.46% efficiency in planar n-Si/PEDOT:PSS hybrid solar cells.

Hybrid organic-inorganic photovoltaic devices consisting of poly(3,4-etyhlenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and n-type silicon have recently been investigated for their cost-efficiency and ease of fabrication. We demonstrate that the insertion of an ultrathin Al2O3 layer between n-Si and PEDOT:PSS significantly improves photovoltaic performance in comparison to the conventional interfacial oxide employing SiO2. A power-conversion efficiency of 11.46% was recorded at the optimal Al2O3 thickness of 2.3 nm. This result was achieved based upon increased built-in potential and improved charge collection via the electron blocking effect of Al2O3. In addition, the hydrophilicity enhanced by Al2O3 improved the coating uniformity of the PEDOT:PSS layer, resulting in a further reduction in surface recombination.

Planar n-Si/PEDOT:PSS hybrid heterojunction solar cells utilizing functionalized carbon nanoparticles synthesized via simple pyrolysis route.

Herein, we present a facile and simple strategy for in situ synthesis of functionalized carbon nanoparticles (CNPs) via direct pyrolysis of ethylenediaminetetraacetic acid (EDTA) on silicon surface. The CNPs were incorporated in hybrid planar n-Si and poly(3,4-etyhlenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) solar cells to improve device performance. We demonstrate that the CNPs-incorporated devices showed increased electrical conductivity (reduced series resistance) and minority carrier lifetime (better charge carrier collection) than those of the cells without CNPs due to the existence of electrically conductive sp 2-hybridized carbon at the heterojunction interfaces. With an optimal concentration of CNPs, the hybrid solar cells exhibited power conversion efficiency up to 11.95%, with an open-circuit voltage of 614 mV, short-circuit current density of 26.34 mA cm-2, and fill factor of 73.93%. These results indicate that our approach is promising for the development of highly efficient organic-inorganic hybrid solar cells.

Toward a planar black silicon technology for 50 µm-thin crystalline silicon solar cells.

Auger and surface recombinations are major drawbacks that deteriorate a photon-to-electron conversion efficiencies in nanostructured (NS) Si solar cells. As an alternative to conventional frontside nanostructuring, we report how backside nanostructuring is beneficial for carrier collection during photovoltaic operation that utilizes a 50-µm-thin wafer. Ultrathin (4.3-nm-thin) zinc oxide was also effective for providing passivated tunneling contacts at the nanostructured backsides, which led to the enhancement of 24% in power conversion efficiency.

Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc-Air Batteries.

The lack of high-efficient, low-cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc-air batteries. A nanocomposite CoO-NiO-NiCo bifunctional electrocatalyst supported by nitrogen-doped multiwall carbon nanotubes (NCNT/CoO-NiO-NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO-NiO-NiCo catalysts further demonstrated superior performance to state-of-the-art Pt/C or Pt/C+IrO2 catalysts in primary and rechargeable zinc-air batteries.

Synergistic effect of carbon nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance all-vanadium redox flow battery.

Carbon nanofiber/nanotube (CNF/CNT) composite catalysts grown on carbon felt (CF), prepared from a simple way involving the thermal decomposition of acetylene gas over Ni catalysts, are studied as electrode materials in a vanadium redox flow battery. The electrode with the composite catalyst prepared at 700 °C (denoted as CNF/CNT-700) demonstrates the best electrocatalytic properties toward the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples among the samples prepared at 500, 600, 700, and 800 °C. Moreover, this composite electrode in the full cell exhibits substantially improved discharge capacity and energy efficiency by ~64% and by ~25% at 40 mA·cm(-2) and 100 mA·cm(-2), respectively, compared to untreated CF electrode. This outstanding performance is due to the enhanced surface defect sites of exposed edge plane in CNF and a fast electron transfer rate of in-plane side wall of the CNT.

Enhancing Li-Ion Battery Anodes: Synthesis, Characterization, and Electrochemical Performance of Crystalline C60 Nanorods with Controlled Morphology and Phase Transition.

Recently, C60 has emerged as a promising anode material for Li-ion batteries, attracting significant interest due to its excellent lithium storage capacity. The electrochemical performance of C60 as an anode is largely dependent on its internal crystal structure, which is significantly influenced by the synthesis method and corresponding conditions. However, there have been few reports on how the synthesis process affects the crystal structure and Li+ storage capacity of C60. This study used the liquid-liquid interface precipitation method and a low-temperature annealing process to fabricate one-dimensional C60 nanorods (NRs). We thoroughly investigated synthesis conditions, including the growth time, drying temperature, annealing time, and annealing atmosphere. The results demonstrate that these synthesis conditions directly impact the morphology, phase transition, and electrochemical efficiency of pure C60 NRs. Remarkably, the hexagonal close-packed structural C60 NRs-6012h, in a metastable form, exhibits a reversible Li+ storage capacity as an anode material in Li-ion batteries. Furthermore, the face-centered cubic C60 NRs-603001h electrode shows significantly enhanced rate performance and long-cycle stability. A discharge-specific capacity of 603 mAh g-1 was maintained after 2000 cycles at a current density of 2 A g-1. This study elucidates the effect of synthesis conditions on C60 crystals, offering an effective strategy for preparing high-performance C60 anode materials.

Structural Engineering of Carbon Host Derived from Organic Pigment toward Physicochemically Confinement and Efficient Conversion of Polysulfide for Lithium-Sulfur Batteries.

Lithium-Sulfur Batteries (LSBs) have attracted significant attention as promising next-generation energy storage systems. However, the commercial viability of LSBs have been hindered due to lithium polysulfides (LiPSs) shuttle effect, resulting in poor cycling stability and low sulfur utilization. To address this issue, herein, the study prepares a sulfur host consisting of micro/mesopore-enriched activated carbonaceous materials with ultrahigh surface area using organic pigment via facile one-step activation. By varying the proportion of chemical agent, the pore size and volume of the activated carbonaceous materials are manipulated and their capabilities on the mitigation of LiPSs shuttle effect are investigated. Through the electrochemical measurements and spectroscopic analysis, it is verified that structural engineering of carbon hosts plays a pivotal role in effective physical confinement of LiPSs, leading to the mitigation of LiPSs shuttle effect and sulfur utilization. Additionally, nitrogen and oxygen-containing functional groups originated from PR show electrocatalytic activation sites, facilitating LiPSs conversion kinetics. The approach can reveal that rational design of carbon microstructures can improve trapping and suppression of LiPSs and shuttle effect, enhancing electrochemical performance of LSBs.

A High Voltage Aqueous Zinc-Vanadium Redox Flow Battery with Bimodal Tin and Copper Clusters by a Continuous-Flow Electrometallic Synthesis.

Aqueous zinc-based redox flow batteries are promising large-scale energy storage applications due to their low cost, high safety, and environmental friendliness. However, the zinc dendritic growth has depressed the cycle performance, stability, and efficiency, hindering the commercialization of the zinc-based redox flow batteries. We fabricate the carbon felt modified with bimodal sized tin and copper clusters (SCCF) with the electrometallic synthesis in a continuous-flow cell. The SCCF electrode provides a larger zinc nucleation area and lower overpotential than pristine carbon felt, which is ascribed to the well-controlled interfacial interaction of bimodal tin and copper particle clusters by suppressing unwanted alloy formation. The zinc symmetric flow battery and the zinc-based hybrid redox flow battery show the improved zinc plating and stripping efficiency. The SCCF electrode exhibits 75% improved cycling stability compared to the pristine carbon felt electrode in the zinc symmetric flow battery. Notably, the high-voltage aqueous zinc-vanadium redox flow battery demonstrates a high average cell voltage of 2.31 V at 40 mA cm-2, showing a Coulombic efficiency of 99.9% and an energy efficiency of 87.6% for 100 cycles. We introduce a facile strategy to suppress the zinc dendritic growth, enhancing the performance of the zinc-based redox flow batteries.

Controllable Carbon Felt Etching by Binary Nickel Bismuth Cluster for Vanadium-Manganese Redox Flow Batteries.

Various redox couples have been reported to increase the energy density and reduce the price of redox flow batteries (RFBs). Among them, the vanadium electrolyte is mainly used due to its high solubility, but electrode modification is still necessary due to its low reversibility and sluggish kinetics. Also, an incompatible ion exchange membrane with redox-active species leads to self-discharge referred to as crossover. Here, we report a V/Mn RFB using an anion exchange membrane (AEM) for crossover mitigation and etched carbon felt by nickel-bismuth (NB-ECF) for the vanadium anolyte. The NB-ECF significantly enhances the reversibility and kinetics of the V2+/V3+ redox reaction, attributed to inhibited irreversible hydrogen evolution by the Bi catalyst and increased carboxyl groups by nickel (etching and NiO catalyst). Notably, the V/Mn cell employed in the NB-ECF maintains a high energy efficiency of 85.7% during 50 cycles without capacity degradation at a current density of 20 mA cm-2, which is attributed to a synergistic effect of crossover mitigation and facilitated V2+/V3+ redox reaction. This study demonstrates the novel electrocatalyst design of carbon felt using two metal species.

Recent Progress in High-voltage Aqueous Zinc-based Hybrid Redox Flow Batteries.

The energy density of redox flow batteries (RFBs) is generally affected by the standard electrode potential and the solubility of the redox active species. These crucial factors are closely related to the solvent in which the active materials are dissolved. Aqueous RFBs have been widely studied due to their excellent reaction kinetics and high solubility of the redox couple in aqueous media. However, the low voltage of conventional aqueous RFBs has hindered them from being candidates for practical applications. Recently, high-voltage aqueous RFBs are implemented based on the low negative potential of the Zn/[Zn(OH)4 ]2- reaction in an alkaline solution. Here, we review recent progress in the design of high energy density RFBs in both aqueous and non-aqueous electrolytes, notably focusing on the Zn/MnO2 hybrid RFBs in detail. Furthermore, strategies for inhibiting zinc dendritic growth and stabilizing manganese redox couple in the RFBs system are discussed.

Low-Index Facet Polyhedron-Shaped Binary Cerium Titanium Oxide for High-Voltage Aqueous Zinc-Vanadium Redox Flow Batteries.

Aqueous zinc-vanadium hybrid redox flow battery systems are an efficient strategy to address the problems of low voltage and high cost of conventional all-vanadium redox flow batteries. However, the low electrochemical activity of carbon-based electrodes toward a vanadium redox reaction limits the performance of redox flow batteries. In this study, polyhedral binary cerium titanium oxide (Ce2/3TiO3, CTO) is synthesized using molten salt synthesis. CTO is fabricated by adjusting the temperature and composition. Notably, the prepared CTO obtained at 1000 °C shows the highest catalytic activity for a VO2+/VO2+ redox reaction. Further, CTO is prepared as a composite electrocatalyst and applied to a high-voltage aqueous zinc-vanadium redox flow battery. The cell adopts an alkali zinc electrolyte containing a Zn/[Zn(OH)4]2- redox pair and exhibits a high operating voltage of 2.26 V. Remarkably, a zinc-vanadium redox flow battery using the composite electrocatalyst exhibits a high energy density of 42.68 Wh L-1 at 20 mA cm-2 and an initial voltage efficiency of 90.3%. The excellent cell performance is attributed to structural defects caused by A-site deficiency in the perovskite oxide structure as well as oxygen vacancies resulting from the low valence state of the metal ion, which enhance the catalytic activity of the vanadium ions.

Material design and surface chemistry for advanced rechargeable zinc-air batteries.

Zinc-air batteries (ZABs) have been considered as a next-generation battery system with high energy density and abundant resources. However, the sluggish multi-step reaction of the oxygen is the main obstacle for the practical application of ZABs. Therefore, bifunctional electrocatalysts with high stability and activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are greatly required to promote the catalytic reaction. In this review, we first explain the reaction mechanism of the ZABs, mainly focusing on multiple oxygen intermediates. Then, the latest studies on bifunctional electrocatalysts for the air cathodes and their progress of the ZABs are discussed with following aspects: platinum group metal, metal-free, transition metal, and metal compound-derived electrocatalysts. Finally, we highlight the advanced ZAB systems with the design of the full-temperature range operation, the all-solid-state, and the newly reported non-alkaline electrolyte, summarizing the remaining challenges and requirements of the future research directions.

Environmentally Compatible Lead-Free Perovskite Solar Cells and Their Potential as Light Harvesters in Energy Storage Systems.

Next-generation renewable energy sources and perovskite solar cells have revolutionised photovoltaics research and the photovoltaic industry. However, the presence of toxic lead in perovskite solar cells hampers their commercialisation. Lead-free tin-based perovskite solar cells are a potential alternative solution to this problem; however, numerous technological issues must be addressed before the efficiency and stability of tin-based perovskite solar cells can match those of lead-based perovskite solar cells. This report summarizes the development of lead-free tin-based perovskite solar cells from their conception to the most recent improvements. Further, the methods by which the issue of the oxidation of tin perovskites has been resolved, thereby enhancing the device performance and stability, are discussed in chronological order. In addition, the potential of lead-free tin-based perovskite solar cells in energy storage systems, that is, when they are integrated with batteries, is examined. Finally, we propose a research direction for tin-based perovskite solar cells in the context of battery applications.

Abnormally High-Lithium Storage in Pure Crystalline C60 Nanoparticles.

Li+ intercalates into a pure face-centered-cubic (fcc) C60 structure instead of being adsorbed on a single C60 molecule. This hinders the excess storage of Li ions in Li-ion batteries, thereby limiting their applications. However, the associated electrochemical processes and mechanisms have not been investigated owing to the low electrochemical reactivity and poor crystallinity of the C60 powder. Herein, a facile method for synthesizing pure fcc C60 nanoparticles with uniform morphology and superior electrochemical performance in both half- and full-cells is demonstrated using a 1 m LiPF6 solution in ethylene carbonate/diethyl carbonate (1:1 vol%) with 10% fluoroethylene carbonate. The specific capacity of the C60 nanoparticles during the second discharge reaches ≈750 mAh g-1 at 0.1 A g-1 , approximately twice that of graphite. Moreover, by applying in situ X-ray diffraction, high-resolution transmission electron microscopy, and first-principles calculations, an abnormally high Li storage in a crystalline C60 structure is proposed based on the vacant sites among the C60 molecules, Li clusters at different sites, and structural changes during the discharge/charge process. The fcc of C60 transforms tetragonal via orthorhombic Lix C60 and back to the cubic phase during discharge. The presented results will facilitate the development of novel fullerene-based anode materials for Li-ion batteries.

Advanced Technologies for High-Energy Aluminum-Air Batteries.

Aluminum-air batteries are considered as next-generation batteries owing to their high energy density with the abundant reserves, low cost, and lightweight of aluminum. However, there are several hurdles to be overcome, such as the sluggish rate of the oxygen reduction reaction (ORR) at the air electrode, precipitation of aluminum hydroxides and oxides at the anode, and severe hydrogen evolution problems at the interface of the anode and the electrolyte. Here, recent advances in silver metal and metal-nitrogen-carbon-based ORR electrocatalysts, aluminum anodes, electrolytes, and the requirements of future research directions are mainly summarized.

Seed-mediated atomic-scale reconstruction of silver manganate nanoplates for oxygen reduction towards high-energy aluminum-air flow batteries.

Aluminum-air batteries are promising candidates for next-generation high-energy-density storage, but the inherent limitations hinder their practical use. Here, we show that silver nanoparticle-mediated silver manganate nanoplates are a highly active and chemically stable catalyst for oxygen reduction in alkaline media. By means of atomic-resolved transmission electron microscopy, we find that the formation of stripe patterns on the surface of a silver manganate nanoplate originates from the zigzag atomic arrangement of silver and manganese, creating a high concentration of dislocations in the crystal lattice. This structure can provide high electrical conductivity with low electrode resistance and abundant active sites for ion adsorption. The catalyst exhibits outstanding performance in a flow-based aluminum-air battery, demonstrating high gravimetric and volumetric energy densities of ~2552 Wh kgAl-1 and ~6890 Wh lAl-1 at 100 mA cm-2, as well as high stability during a mechanical recharging process.

Exploring Critical Factors Affecting Strain Distribution in 1D Silicon-Based Nanostructures for Lithium-Ion Battery Anodes.

Despite the advantage of high capacity, the practical use of the silicon anode is still hindered by large volume expansion during the severe pulverization lithiation process, which results in electrical contact loss and rapid capacity fading. Here, a combined electrochemical and computational study on the factor for accommodating volume expansion of silicon-based anodes is shown. 1D silicon-based nanostructures with different internal spaces to explore the effect of spatial ratio of voids and their distribution degree inside the fibers on structural stability are designed. Notably, lotus-root-type silicon nanowires with locally distributed void spaces can improve capacity retention and structural integrity with minimum silicon pulverization during lithium insertion and extraction. The findings of this study indicate that the distribution of buffer spaces, electrochemical surface area, as well as Li diffusion property significantly influence cycle performance and rate capability of the battery, which can be extended to other silicon-based anodes to overcome large volume expansion.

Controllable Solid Electrolyte Interphase in Nickel-Rich Cathodes by an Electrochemical Rearrangement for Stable Lithium-Ion Batteries.

The layered nickel-rich materials have attracted extensive attention as a promising cathode candidate for high-energy density lithium-ion batteries (LIBs). However, they have been suffering from inherent structural and electrochemical degradation including severe capacity loss at high electrode loading density (>3.0 g cm-3 ) and high temperature cycling (>60 °C). In this study, an effective and viable way of creating an artificial solid-electrolyte interphase (SEI) layer on the cathode surface by a simple, one-step approach is reported. It is found that the initial artificial SEI compounds on the cathode surface can electrochemically grow along grain boundaries by reacting with the by-products during battery cycling. The developed nickel-rich cathode demonstrates exceptional capacity retention and structural integrity under industrial electrode fabricating conditions with the electrode loading level of ≈12 mg cm-2 and density of ≈3.3 g cm-3 . This finding could be a breakthrough for the LIB technology, providing a rational approach for the development of advanced cathode materials.