Rechargeable lithium metal batteries are considered the "Holy Grail" of energy storage systems. Unfortunately, uncontrollable dendritic lithium growth inherent in these batteries (upon repeated charge/discharge cycling) has prevented their practical application over the past 40 years. We show a novel mechanism that can fundamentally alter dendrite formation. At low concentrations, selected cations (such as cesium or rubidium ions) exhibit an effective reduction potential below the standard reduction potential of lithium ions. During lithium deposition, these additive cations form a positively charged electrostatic shield around the initial growth tip of the protuberances without reduction and deposition of the additives. This forces further deposition of lithium to adjacent regions of the anode and eliminates dendrite formation in lithium metal batteries. This strategy may also prevent dendrite growth in lithium-ion batteries as well as other metal batteries and transform the surface uniformity of coatings deposited in many general electrodeposition processes.
The lithium-air battery is one of the most promising technologies among various electrochemical energy storage systems. We demonstrate that a novel air electrode consisting of an unusual hierarchical arrangement of functionalized graphene sheets (with no catalyst) delivers an exceptionally high capacity of 15000 mAh/g in lithium-O(2) batteries which is the highest value ever reported in this field. This excellent performance is attributed to the unique bimodal porous structure of the electrode which consists of microporous channels facilitating rapid O(2) diffusion while the highly connected nanoscale pores provide a high density of reactive sites for Li-O(2) reactions. Further, we show that the defects and functional groups on graphene favor the formation of isolated nanosized Li(2)O(2) particles and help prevent air blocking in the air electrode. The hierarchically ordered porous structure in bulk graphene enables its practical applications by promoting accessibility to most graphene sheets in this structure.
N anocomposites have attracted wide attention because of their potential to combine desirable properties of different nanoscale building blocks to improve mechanical, optical, electronic , or magnetic properties. 16 Most traditional synthesis approaches of nanocom-posites rely on mechanical or chemical mixing and produce a random distribution of the constitutive phases. To address these problems, several groups recently investigated layer-by-layer deposition and other techniques to prepare layered nanocom-posites with ceramics, clays, and graphite oxide nanoplatelets, 79 but these methods are lacking in nanoscale spatial precision and are time-consuming and difficult for bulk-materials synthesis. On the other hand, biological systems abound with nanocom-posites that possess well-controlled archi-tectures based on multiple scale and multi-functional building blocks. 10 One powerful approach to achieve similar control is to use amphiphilic polymer or surfactant to direct the self-assembly of nanostructured metal oxides, semiconductors, and polymer materials. 1115 There has been a growing interest in incorporating functional components , such as functional groups, polymers, and nanoparticles, into the self-assembled nanostructures, but success has been limited to two-phase organic/inorganic hybrid materials, nanoparticles, or polymer-based nanocomposites. 4,5,16,17 Recently, a range of nanoscale building blocks, including carbon nanotubes 1821 and graphene, 2224 have gained prominence. Graphene and graphene stacks (mul-tilayer graphene), potentially low cost alternative materials to single-wall or multiwall carbon nanotubes, have unique electronic conductivity and mechanical properties. 2527 Graphene-based nanocom-posites with polymer, metal, or metal oxides have also shown unique mechanical, electronic , and electrochemical properties. 23,2835 We focus on the nano-composites made of metal oxides (i.e., SnO 2 , NiO, MnO 2 , and SiO 2) that could have important applications for electrochemical energy storage. 36,37 The low conductivity and poor stability of such materials usually necessitate adding conductive phases to enhance electron transport and electrical contact of the active materials in the electrode of a Li-ion battery. In most of these studies, the approach used to prepare the composite materials has been mechanical mixing of metal oxides with conductive materials such as amorphous carbon, carbon nano-tubes, and graphene. 31,38 In spite of these studies, a well-controlled architecture of the conductive material and metal oxide is difficult to achieve because of improper ABSTRACT Surfactant or polymer directed self-assembly has been widely investigated to prepare nanostructured metal oxides, semiconductors, and polymers, but this approach is mostly limited to two-phase materials, organic/inorganic hybrids, and nanoparticle or polymer-based nanocomposites. Self-assembled nanostructures from more complex, multiscale, and multiphase building blocks have been investigated with limited success. Here, we demonstr...
The all-vanadium redox fl ow battery is a promising technology for large-scale renewable and grid energy storage, but is limited by the low energy density and poor stability of the vanadium electrolyte solutions. A new vanadium redox fl ow battery with a signifi cant improvement over the current technology is reported in this paper. This battery uses sulfate-chloride mixed electrolytes, which are capable of dissolving 2.5 M vanadium, representing about a 70% increase in energy capacity over the current sulfate system. More importantly, the new electrolyte remains stable over a wide temperature range of − 5 to 50 ° C, potentially eliminating the need for electrolyte temperature control in practical applications. This development would lead to a signifi cant reduction in the cost of energy storage, thus accelerating its market penetration.
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