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At least 163 records · Page 9

Anode-Free Rechargeable Lithium Metal Batteries

Anode-free rechargeable lithium (Li) batteries (AFLBs) are phenomenal energy storage systems due to their significantly increased energy density and reduced cost relative to Li-ion batteries, as well as ease of assembly owing to the absence of an active (reactive) anode material. However, significant challenges, including Li dendrite growth and low cycling Coulombic efficiency (CE), have prevented their practical implementation. Here, we report for the first time an anode-free rechargeable lithium battery based on a Cu||LiFePO4 cell structure with an extremely high CE (> 99.8%). This results from the utilization of both an exceptionally stable electrolyte and optimized charge/discharge protocols which minimize the corrosion of the in-situ formed Li metal anode.

anode-free↗

High Depth‐of‐Discharge Zinc Rechargeability Enabled by a Self‐Assembled Polymeric Coating

Abstract Zinc has the potential for widespread use as an environmentally friendly and cost‐effective anode material pending the resolution of rechargeability issues caused by active material loss and shape change. Here, a self‐assembled Nafion‐coated Celgard 3501 (NC‐Celgard) separator is shown to enable unprecedented cycle life of a Zn anode in alkaline electrolyte at high depth‐of‐discharge (DOD Zn ). Using commercially relevant energy‐dense electrodes with high areal capacities of 60 mAh cm –2 , Zn–Ni cells tested at 20% DOD Zn cells achieve over 200 cycles while 50% DOD Zn cells achieve over 100 cycles before failure. The 20% and 50% DOD cells deliver an average of 132 and 180 Wh L –1 per cycle over their lifetime respectively. Rechargeability is attributed to the highly selective diffusion properties of the 300 nm thick negatively charged Nafion coating on the separator which prevents shorting by dendrites and inhibits redistribution of the active material. Crossover experiments show that the NC‐Celgard separator is practically impermeable to zincate ([Zn(OH) 4 ] 2– ), outperforming commercial Celgard, cellophane, Nafion 211 and 212 separators while still allowing hydroxide transport. This work demonstrates the efficacy of selective separators for increasing the cycle life of energy‐dense Zn electrodes without adding significant volume or complexity to the system.

Arnot, David J.↗

A Rechargeable Al/S Battery with an Ionic‐Liquid Electrolyte

Abstract Aluminum metal is a promising anode material for next generation rechargeable batteries owing to its abundance, potentially dendrite‐free deposition, and high capacity. The rechargeable aluminum/sulfur (Al/S) battery is of great interest owing to its high energy density (1340 Wh kg −1 ) and low cost. However, Al/S chemistry suffers poor reversibility owing to the difficulty of oxidizing AlS x . Herein, we demonstrate the first reversible Al/S battery in ionic‐liquid electrolyte with an activated carbon cloth/sulfur composite cathode. Electrochemical, spectroscopic, and microscopic results suggest that sulfur undergoes a solid‐state conversion reaction in the electrolyte. Kinetics analysis identifies that the slow solid‐state sulfur conversion reaction causes large voltage hysteresis and limits the energy efficiency of the system.

Gao, Tao↗

An Efficient Rechargeable Aluminium–Amine Battery Working Under Quaternization Chemistry

Rechargeable aluminium (Al) batteries (RABs) have long-been pursued due to the high sustainability and three-electron-transfer properties of Al metal. However, limited redox chemistry is available for rechargeable Al batteries, which restricts the exploration of cathode materials. Herein, we demonstrate an efficient Al–amine battery based on a quaternization reaction, in which nitrogen (radical) cations (R 3 N .+ or R 4 N + ) are formed to store the anionic Al complex. The reactive aromatic amine molecules further oligomerize during cycling, inhibiting amine dissolution into the electrolyte. Consequently, the constructed Al–amine battery exhibits a high reversible capacity of 135 mAh g -1 along with a superior cycling life (4000 cycles), fast charge capability and a high energy efficiency of 94.2 %. Moreover, the Al–amine battery shows excellent stability against self-discharge, far beyond conventional Al–graphite batteries. Our findings pave an avenue to advance the chemistry of RABs and thus battery performance.

25 ENERGY STORAGE↗

Selenium Nanocomposite Cathode with Long Cycle Life for Rechargeable Lithium‐Selenium Batteries

Abstract Selenium (Se) is a potential cathode material for high energy density rechargeable lithium batteries. In this study, a binder‐free Se‐carbon nanotube (CNT) composite electrode has been prepared by a facile chemical method. At initial state, Se is present in the form of branched nanowires with a diameter of <150 nm and a length of 1–2 μm, interwoven with CNTs. After discharge and re‐charge, the Se nanowires are converted to nanoparticles embedded in the CNT network. This synthesis method provides a path for fabricating the Se cathodes with controllable mass loading and thickness. By studying the composite electrodes with different Se loading and thickness, we found that the electrode thickness has a critical impact on the distribution of Se during repeated cycling. Promising cycling performance was achieved in thin electrodes with high Se loading. The composite electrode with 23 μm thickness and 60 % Se loading shows a high initial capacity of 537 mAh g −1 and stable cycling performance with a capacity of 401 mAh g −1 after 500 cycles at 1 C rate. This study reports a synthesis strategy to obtain Se/CNT composite cathode with long cycle life for rechargeable Li−Se batteries.

Cui, Yi↗

Bipolar Organic Cathodes for Stable and Sustainable Na‐Ion and Rechargeable Al Batteries

Bipolar organic materials have emerged as promising cathode materials for rechargeable batteries because of their high voltage and high capacity. However, they suffer from poor cyclic stability and slow reaction kinetics. In this work, we designed and synthesized two bipolar organic cathode materials, containing carbonyl (n‐type) and amine (p‐type) functional groups, as well as extended conjugation structures, for Na‐ion batteries (NIBs) and rechargeable aluminum batteries (RABs). As universal electrode materials, bipolar organic materials exhibited exceptional electrochemical performance in terms of high capacity, high voltage, long cycle life, and fast rate capability. Further, the extended conjugation structures in backbones of the bipolar organic materials facilitate the π–π stacking with graphene, playing a critical role in the high performance. Furthermore, the formation of a stable and robust NaF‐rich cathode electrolyte interphase was shown to stabilize the bipolar organic cathode in NIBs. Electrochemical kinetic measurements reveal that both functional groups undergo reversible redox reactions. Specifically, the electron transfer rate constant of the p‐type amine group is one order of magnitude higher than that of the n‐type carbonyl group. These results highlight the efficacy of developing bipolar organic materials for achieving high‐performance organic cathode in NIBs and RABs.

25 ENERGY STORAGE↗

Ionic Liquid–Directed Nanoporous TiNb 2 O 7 Anodes with Superior Performance for Fast–Rechargeable Lithium–Ion Batteries

Nanoporous TiNb 2 O 7 (NPTNO) material is synthesized by a sol–gel method with an ionic liquid (IL) as the nanoporous structure directing template. NPTNO exhibits a high reversible capacity of 210 mAh g –1 even at the charging rate of 50 C and an excellent cyclability of half-cell capacity retention of 74% for 1000 cycles at 5 C and LiNi 0.5 Mn 1.5 O 4 -coupled full-cell capacity retentions of 81% and 87% for 1000 cycles at 1 C and 2 C, respectively. The studies of the 1000 cycled NPTNO electrode illustrate that the IL-directed mesoporous structure can enhance the cyclability of NPTNO cells due to the alleviation of repetitive mechanical stress and volume fluctuation induced by the repetitive Li + insertion-extraction processes. The measured Li + diffusion coefficients from the galvanostatic intermittent titration technique suggest that the IL-templating strategy indeed ensures the fast rechargeability of NPTNO cells based on the fast Li + diffusion kinetics. Benefitting from the nanoporous structure, NPTNO with unhindered Li + diffusion pathways achieves a superior rate capability in the titanium-based oxide materials and the best full-cell cyclability in the TNO materials. Furthermore, the templating potential of IL is demonstrated, and the superb electrochemical performance establishes the IL-directed NPTNO as a promising anode candidate for fast-rechargeable LIBs.

25 ENERGY STORAGE↗

Assessing the recharge process and importance of montane water to adjacent tectonic valley-plain groundwater using a ternary end-member mixing analysis based on isotopic and chemical tracers

A study in eastern Taiwan evaluated the importance of montane water contribution (MC) to adjacent valley-plain groundwater (VPG) in a tectonic suture zone. The evaluation used a ternary natural-tracer-based end-member mixing analysis (EMMA). With this purpose, VPG and three end-member water samples of plain precipitation (PP), mountain-front recharge (MFR), and mountain-block recharge (MBR) were collected and analyzed for stable isotopic compositions (δ{sup 2}H and δ{sup 18}O) and chemical concentrations (electrical conductivity (EC) and Cl{sup −}). After evaluation, Cl{sup −} is deemed unsuitable for EMMA in this study, and the contribution fractions of respective end members derived by the δ{sup 18}O–EC pair are similar to those derived by the δ{sup 2}H–EC pair. EMMA results indicate that the MC, including MFR and MBR, contributes at least 70% (679 × 10{sup 6} m{sup 3} water volume) of the VPG, significantly greater than the approximately 30% of PP contribution, and greater than the 20–50% in equivalent humid regions worldwide. The large MC is attributable to highly fractured strata and the steep topography of studied catchments caused by active tectonism. Furthermore, the contribution fractions derived by EMMA reflect the unique hydrogeological conditions in the respective study sub-regions. A region with a large MBR fraction is indicative of active lateral groundwater flow as a result of highly fractured strata in montane catchments. On the other hand, a region characterized by a large MFR fraction may possess high-permeability stream beds or high stream gradients. Those hydrogeological implications are helpful for water resource management and protection authorities of the studied regions.

58 GEOSCIENCES↗

Rapid microwave-assisted preparation of high-performance bifunctional Ni3Fe/Co-N-C for rechargeable Zn-air battery

Precious metal-free bifunctional catalysts offer scalable possibilities for achieving oxygen cathodes in rechargeable metal-air batteries. Literature thus far suggests that the oxygen reduction and evolution reactions (i.e ORR and OER) take place at different active sites. However, the design and preparation of oxygen electrocatalysts with high-performance is still a great challenge. This work develops a general approach to introduce a nanoparticle that offers oxygen evolution reaction sites onto an oxygen reduction reaction catalyst via rapid microwave treatment. The metal–organic frameworks (Co, ZIF-8) derived Co-N-C with high ORR performance is employed as a support to homogeneously disperse OER active Ni3Fe nanoparticles. Potentials of 1.54 V and 0.79 V have been achieved at current densities of 10 mA cm -2 for OER and 3 mA cm -2 toward ORR, respectively. The developed rechargeable Zn-air battery assembled with Ni 3 Fe/Co-N-C as an oxygen-electrode exhibits superior efficiency and robust durability, exceeding that of commercial Pt/C + IrO 2 . Furthermore, the satisfactory activity of our fabricated wristband shows the successfully practical application of flexible Zn-air batteries for wearable devices.

25 ENERGY STORAGE↗

Field experiments of surface water to groundwater recharge to characterize the mobility of uranium and vanadium at a former mill tailing site

Characterizing the mobility of uranium and vanadium in groundwater with a hydraulic connection to surface water is important to inform the best management practices of former mill tailing sites. In this study, the recharge of river water to the unsaturated and saturated zones of a uranium-contaminated alluvial aquifer was simulated in a series of forced-gradient single- and multi-well injection-extraction tests. The injection fluid (river water) was traced with natural and artificial tracers that included halides, fluorobenzoates, lithium, and naphthalene sulfonate to characterize the potential mass transport mechanisms of uranium and vanadium. The extraction fluid (river water/groundwater mixture) was analyzed for the tracers, uranium, and vanadium. The results from the tracers indicated that matrix diffusion was likely negligible over the spatiotemporal scales of the tests as evident by nearly identical breakthrough curves of the halides and fluorobenzoates. In contrast, the breakthrough curves of lithium and naphthalene sulfonate indicated that sorption by cation exchange and sorption to organic matter, respectively, were potential mass transport mechanisms of uranium and vanadium. Uranium was mobilized in the saturated zone containing gypsum (gypsum-rich zone), the vadose zone (vadose-rich zone), and the saturated zone containing organic carbon (organic-rich zone) whereas vanadium was mobilized only in the saturated gypsum-rich zone. The mechanisms responsible for the mobilization of uranium and vanadium were likely dissolution of uranium- and vanadium-bearing minerals and/or desorption from the gypsum-rich zone, flushing of uranium from the vadose-rich zone, and desorption of uranium from the organic-rich zone due to the natural contrast in the geochemistry between the river water and groundwater. The experimental design of this study was unique in that it employed the use of multiple natural and artificial tracers coupled with a direct injection of native river water to groundwater. Here, these results demonstrated that natural recharge and flooding events at former mill tailing sites can mobilize uranium, and possibly vanadium, and contribute to persistent levels of groundwater contamination.

54 ENVIRONMENTAL SCIENCES↗

Evaluation of slurry characteristics for rechargeable lithium-ion batteries

Graphical abstract: - Highlights: • Lithium-ion battery slurries are prepared for rechargeable batteries. • The dispersion state of slurry constituents is identified. • Thermal, morphological, rheological, and electrical properties of slurries are analyzed. - Abstract: A multi-component slurry for rechargeable batteries is prepared by dispersing LiCoO{sub 2}, conductive additives, and polymeric binders in a solvent. The physical properties, including rheological, morphological, electrical, and spectroscopic features of battery slurries are investigated. The relationship between the measured physical properties and the internal structure of the slurry is analyzed. It is found that the rheological behavior of the slurry is determined by the interaction of active materials and binding materials (e.g., network structure) and that the dispersion state of conductive additives (e.g., agglomeration) also depends on the binder–carbon interaction.

36 MATERIALS SCIENCE↗

Electronic tuning of confined sub-nanometer cobalt oxide clusters boosting oxygen catalysis and rechargeable Zn–air batteries.

Reasonable design of robust bifunctional oxygen catalysts from an electronic structure perspective is intriguing and challenging for the development of high active rechargeable zinc-air batteries (ZABs). In this study, the favorable regulation of the electronic structure of the cobalt oxide nanoclusters was firstly predicted by density functional theory (DFT) simulation, and then experimentally verified by confining sub-nanometer CoOx clusters (0.86 nm) into the small pore of ZIF-8 derived N-doped nanomaterials (PNC) using a microporous MOFs confinement strategy. The confined effect of the MOF micropores not only enhanced the stability of the subnanometer cobalt oxide clusters, but also make it coupled with Co-Nx to further regulate the electronic structure of the former, synergistic resulting in enhanced ORR/OER actives. As a result, the optimized 0.05CoOx@PNC catalyst demonstrates outstanding bifunctional oxygen performance with a smaller potential gap of 0.67 V. Moreover, the rechargeable Zn-air batteries integrated 0.05CoOx@PNC air cathode displays encouraging performance with a peak power density of 157.1 mW cm(-2), a specific capacity of 887 mAh g(Zn)(-1)at 10 mA cm(-2) and long-term cyclability for over 200 h, significantly outperforming the benchmark electrode couple consisted of Pt/C/RuO2. DFT calculation further revealed that reducing particle size and coupling with Co-N could effectively regulate the charge distribution of CoOx nanoclusters and downshift the D-band center of Co adsorption sites in CoOx nanoclusters, which reduced the reaction barrier of intermediate O-2* and OH* and ORR/ OER over potential, thus accelerating the overall ORR/OER kinetic process. This work offers a novel reference for the construction of a robust sub-nanometer cluster catalysts in the field of ZABs.

Bifunctional oxygen electrocatalysts↗

Defect-Engineered High-Entropy Spinel Oxide@Onion-Like Carbon Catalysts for High-Areal-Energy Rechargeable Zinc–Air Batteries

Rechargeable zinc-air batteries (ReZAB) have emerged as the next-generation batteries with several advantages over the conventional lithium-ion battery. In this work, single nanocrystals of inverse-type high-entropy spinel oxides (HESOx, particle size of 10−12 nm) confined in highly curved defective onion-like carbons (HESOx/OLC AT ) as efficient electrocatalysts for oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and ReZAB, have been synthesized. The HESOx materials were thoroughly characterized using several analytical techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), Raman, and electron paramagnetic resonance (EPR). HESOx/OLC AT catalyst was tested for ReZAB using literature-recommended parameters that would allow for real technological application. These parameters include a current loading of 10 mA cm −2 and a discharge areal energy density of 35 mWh cm geometric −2 , which maps a Li-ion battery pack-level specific energy of 120 Wh kg pack −1 . HESOx/OLC AT electrocatalysts allowed for continuous discharging and charging at a current loading of 10 mA cm −2 with discharge areal energy densities between 37 and 74 mWh cm geometric −2 , thus outperforming the recommended threshold of 35 mWh cm geometric −2 . Considering that most studies (>90%) hardly meet the recommended threshold for technological application of ReZAB, the present work represents one of the top-performing electrocatalysts for ReZAB. The excellent electrocatalytic properties of defect-rich HESOx/OLC AT toward ORR/OER and ReZAB are governed by the strong electronic modulation arising from d-π hybridization, the availability of multiple catalytic sites for intermediates, and weakened d-band centers of the rate-determining intermediates (i.e., *O adsorption for ORR and *OOH formation for OER) compared to the pristine HESOx. This work introduces an effective approach for the design and synthesis of single nanocrystals of high-entropy electrocatalysts for the development of low-cost, robust, and technologically relevant rechargeable zinc−air batteries.

25 ENERGY STORAGE↗

Binder-Free V 2 O 5 Cathode for Greener Rechargeable Aluminum Battery

This letter reports on the investigation of a binder-free cathode material to be used in rechargeable aluminum batteries. This cathode is synthesized by directly depositing V2O5 on a Ni foam current collector. Rechargeable aluminum coin cells fabricated using the as-synthesized binder-free cathode delivered an initial discharge capacity of 239 mAh/g, which is much higher than that of batteries fabricated using a cathode composed of V2O5 nanowires and binder. An obvious discharge voltage plateau appeared at 0.6 V in the discharge curves of the Ni–V2O5 cathode, which is slightly higher than that of the V2O5 nanowire cathodes with common binders. This improvement is attributed to reduced electrochemical polarization.

aluminum battery↗

Nanostructured bilayered vanadium oxide electrodes for rechargeable sodium-ion batteries.

Tailoring nanoarchitecture of materials offers unprecedented opportunities in utilization of their functional properties. Nanostructures of vanadium oxide, synthesized by electrochemical deposition, are studied as a cathode material for rechargeable Na-ion batteries. Ex situ and in situ synchrotron characterizations revealed the presence of an electrochemically responsive bilayered structure with adjustable intralayer spacing that accommodates intercalation of Na{sup +} ions. Sodium intake induces organization of overall structure with appearance of both long- and short-range order, while deintercalation is accompanied with the loss of long-range order, whereas short-range order is preserved. Nanostructured electrodes achieve theoretical reversible capacity for Na{sub 2}V{sub 2}O{sub 5} stoichiometry of 250 mAh/g. The stability evaluation during charge-discharge cycles at room temperature revealed an efficient 3 V cathode material with superb performance: energy density of {approx}760 Wh/kg and power density of 1200 W/kg. These results demonstrate feasibility of development of the ambient temperature Na-ion rechargeable batteries by employment of electrodes with tailored nanoarchitectures.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

The facile conduction of alkali ions in a crystal host is of crucial importance in rechargeable alkali-ion batteries, the dominant form of energy storage today. In this review, we provide a comprehensive survey of computational approaches to study solid-state alkali diffusion. We demonstrate how these methods have provided useful insights into the design of materials that form the main components of a rechargeable alkali-ion battery, namely the electrodes, superionic conductor solid electrolytes and interfaces. We will also provide a perspective on future challenges and directions. Here, the scope of this review includes the monovalent lithium- and sodium-ion chemistries that are currently of the most commercial interest.

25 ENERGY STORAGE↗

Lithium Metal Anodes for Rechargeable Batteries

Rechargeable lithium metal batteries have much higher energy density than those of lithium ion batteries using graphite anode. Unfortunately, uncontrollable dendritic lithium growth inherent in these batteries (upon repeated charge/discharge cycling) and limited Coulombic efficiency during lithium deposition/striping has prevented their practical application over the past 40 years. With the emerging of post Li-ion batteries, safe and efficient operation of lithium metal anode has become an enabling technology which may determine the fate of several promising candidates for the next generation of energy storage systems, including rechargeable Li-air battery, Li-S battery, and Li metal battery which utilize lithium intercalation compounds as cathode. In this work, various factors which affect the morphology and Coulombic efficiency of lithium anode will be analyzed. Technologies used to characterize the morphology of lithium deposition and the results obtained by modeling of lithium dendrite growth will also be reviewed. At last, recent development in this filed and urgent need in this field will also be discussed.

25 ENERGY STORAGE↗

A Facile Approach Using MgCl2 to Formulate High Performance Mg2+ Electrolytes for Rechargeable Mg Batteries

Rechargeable Mg batteries have been regarded as a viable battery technology for grid scale energy storage and transportation applications. However, the limited performance of Mg2+ electrolytes has been a primary technical hurdle to develop high energy density rechargeable Mg batteries. In this study, MgCl2 is demonstrated as a non-nucleophilic and cheap Mg2+ source in combining with Al Lewis acids (AlCl3, AlPh3 and AlEtCl2) to formulate a series of Mg2+ electrolytes characteristic of high oxidation stability (up to 3.4 V vs Mg), sulfur compatibility and electrochemical reversibility (up to 100% coulombic efficiency). Three electrolyte systems (MgCl2-AlCl3, MgCl2-AlPh3, and MgCl2-AlEtCl2) were prepared free of purification and fully characterized by multinuclear NMR (27Al{1H} and 25Mg{1H}) spectroscopies, single crystal X-ray diffraction, and electrochemical analysis. The reaction mechanism of MgCl2 and the Al Lewis acids in THF is discussed to highlight the formation of the electrochemically active [(µ-Cl)3Mg2(THF)6]+ monocation in these electrolytes. We are grateful for the financial support from the Pacific Northwest National Laboratory (PNNL)-Laboratory Directed Research and Development (LDRD) program for developing magnesium battery technology. The XRD and SEM data were collected at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is a multiprogram laboratory operated by Battelle Memorial Institute for the Department of Energy under Contract DE-AC05-76RL01830.

electrolytes↗