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The degradation of current Li-ion batteries (LIBs) hinders their use in electronic devices, electric vehicles, and other applications at low temperatures, particularly in extreme environments like the polar regions and outer space. This study presents a pseudocapacitive-type niobium tungsten oxides (NbWO) electrode material combined with tailored electrolytes, enabling extreme low-temperature battery cycling for the first time. The synthesized NbWO material exhibits analogous structural properties to previous studies. Its homogenous atom distribution can further facilitate Li+ diffusion, while its pseudocapacitive Li+ storage mechanism enables faster Li+ reactions. Notably, the NbWO electrode material exhibits remarkable battery performance even at -60 and -100 °C, showcasing capacities of ≈90 and ≈75 mAh g-1 , respectively. The electrolytes, which have demonstrated favorable Li+ transport attributes at low temperatures in the earlier investigations, now enable extreme low-temperature battery operations, a feat not achievable with either NbWO or the electrolytes independently. Moreover, the outcomes extend to -120 °C and encompass a pouch-type cell configuration at -100 °C, albeit with reduced performance. This study highlights the potential of NbWO for developing batteries for their use in extremely frigid environments.
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Lithium-sulfur (Li-S) batteries hold immense promise as next-generation energy storage due to their high theoretical energy density (2600 Wh kg⻹), low cost, and non-toxic nature. However, practical implementation faces challenges, primarily from Li polysulfide (LiPS) shuttling within the cathode and Li dendrite growth at the anode. Optimized electrodes/electrolytes design effectively confines LiPS to the cathode, boosting cycling performance in coin cells to up to hundreds of cycles. Scaling up to larger pouch cells presents new obstacles, requiring further research for long-term stability. A 1.45 Ah pouch cell, with optimized sulfur loading and electrolyte/sulfur ratio is developed, which delivers an energy density of 151 Wh kg-1 with 70% capacity retention up to 100 cycles. Targeting higher energy density (180 Wh kg-1), the developed 1Ah pouch cell exhibits 68% capacity retention after 50 cycles. Morphological analysis reveals that pouch cell failure is primarily from Li metal powdering and resulting polarization, rather than LiPS shuttling. This occurs for continuous Li ion stripping/plating during cycling, leading to dendrite growth and formation of non-reactive Li powder, especially under high currents. These issues increase ion diffusion resistance and reduce coulombic efficiency over time. Therefore, the study highlights the importance of a protected Li metal anode for achieving high-energy-dense batteries.
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Transition-metal oxide nanostructured materials are potentially attractive alternatives as anodes for Li ion batteries and as photocatalysts. Combining the structural and thermal stability of titanium oxides with the relatively high oxidation potential and charge capacity of molybdenum(VI) oxides was the motivation for a search for approaches to mixed oxides of these two metals. Challenges in traditional synthetic methods for such materials made development of a soft chemistry single-source precursor pathway our priority. A series of bimetallic Ti-Mo alkoxides were produced by reactions of homometallic species in a 1:1 ratio. Thermal solution reduction with subsequent reoxidation by dry air offered in minor yields Ti2Mo2O4(OMe)6(OiPr)6 (1) by the interaction of Ti(OiPr)4 with MoO(OMe)4 and Ti6Mo6O22(OiPr)16(iPrOH)2 (2) by the reaction of Ti(OiPr)4 with MoO(OiPr)4. An attempt to improve the yield of 2 by microhydrolysis, using the addition of stoichiometric amounts of water, resulted in the formation with high yield of a different complex, Mo7Ti7+xO31+x(OiPr)8+2x (3). Controlled thermal decomposition of 1-3 in air resulted in their transformation into the phase TiMoO5 (4) with an orthorhombic structure in space group Pnma, as determined by a Rietveld refinement. The electrochemical characteristics of 4 and its chemical transformation on Li insertion were investigated, showing its potential as a promising anode material for Li ion batteries for the first time. A lower charge capacity and lower stability were observed for its application as an anode for a Na ion battery.
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Solid-state ion shuttles are of broad interest in electrochemical devices, nonvolatile memory, neuromorphic computing, and biomimicry utilizing synthetic membranes. Traditional design approaches are primarily based on substitutional doping of dissimilar valent cations in a solid lattice, which has inherent limits on dopant concentration and thereby ionic conductivity. Here, we demonstrate perovskite nickelates as Li-ion shuttles with simultaneous suppression of electronic transport via Mott transition. Electrochemically lithiated SmNiO3 (Li-SNO) contains a large amount of mobile Li+ located in interstitial sites of the perovskite approaching one dopant ion per unit cell. A significant lattice expansion associated with interstitial doping allows for fast Li+ conduction with reduced activation energy. We further present a generalization of this approach with results on other rare-earth perovskite nickelates as well as dopants such as Na+ The results highlight the potential of quantum materials and emergent physics in design of ion conductors.
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As a novel anodic electrode for Li-ion storage, the cubic Bi4Ge3O12 phase can experimentally deliver a remarkably high reversible specific capacity of 586 mA h g-1 at 200 mA h g-1 with a coulombic efficiency of 99.8% after 500 cycles, and has recently attracted attention for its stable electrochemical performance. Here we calculated its lithiation/delithiation reactions by using density functional theory studies, through the structural changes as the conversion and alloying reaction takes place during the Li-ion insertion and extraction process. The obtained theoretical capacity of Li is 48.75 mol (â¼1043 mA h g-1) for 1 mol Bi4Ge3O12. The decomposed Bi2O3 (P3[combining macron]m1) and GeO2 (P3121) in the lithiation process of Bi4Ge3O12 are the active materials to react with the Li atoms via a conversion reaction. Besides Li2O with both Fm3[combining macron]m and Pnma phases, the final lithiation products of Bi4Ge3O12 should include Li3Bi (Fm3[combining macron]m) and Li4.25Ge (F4[combining macron]3m), through the alloying reactions of multi-valence elements of Bi and Ge with Li. Bi and Ge metals are also helpful in the decomposition of Li2O into Li during the delithiation process, increasing the reversibility of the conversion reactions. Our research provides theoretical support to understand the working mechanism of Bi4Ge3O12 and related mixed-metal anode materials.
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This work provides an alternative solution to the challenge of battery recycling via the upcycling of spent lithium cobalt oxide (LCO) as a new promising solid lubricant additive. An advanced solid lubricant mixture of graphene, Aremco binder, and recycled LCO was formulated into a spray with the use of excess volatile organic solvent. Numerous flat steel disks were spray-coated with the new lubricant formulation and naturally dried followed by curing at 180 °C. When tested on a ball-on-disk up to 230 m in distance, the composite new solid lubricant reduced the coefficient of friction (COF) by 85% between two steel surfaces compared to unlubricated surfaces under a constant 1 GPa Hertzian pressure in an ambient environment. The tribofilm composition, particle size, and type of contact are identified as important parameters in the improvement of the COF. Scanning electron microscopy was used to study its morphology, and energy dispersive X-ray spectroscopy was used to analyze the composition of pristine and tested tribofilms. Upcycled spent low value LCO powder was used as a lubricant additive in tribology for the first time with exceptional lubricious properties.
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Cobalto , Litio , Electrodos , Lubricantes , ÓxidosRESUMEN
A scalable, solid-state elevated-temperature process was developed to produce high-capacity carbonaceous electrode materials for energy storage devices via decomposition of a starch-based precursor in an inert atmosphere. In a separate study, it is shown that the fabricated carbonaceous architectures are useful as an excellent electrode material for lithium-ion, sodium-ion, and lithium-sulfur batteries. This article focuses on the study and analysis of the formed nanometer-sized by-products during the lab-scale synthesis of the carbon material. The material production process was studied in operando (that is, during the entire duration of heat treatment). The unknown downstream particles in the process exhaust were collected and characterized via aerosol and liquid suspensions, and they were quantified using direct-reading instruments for number and mass concentrations. The airborne emissions were collected using the Tsai diffusion sampler (TDS) for characterization and further analysis. Released by-product aerosols collected in a deionized (DI) water trap were analyzed, and the aerosols emitted from the post-water-suspension were collected and characterized. After long-term sampling, individual particles in the nanometer size range were observed in the exhaust aerosol with layer-structured aggregates formed on the sampling substrate. Upon the characterization of the released aerosol by-products, methods were identified to mitigate possible human and environmental exposures upon industrial implementation.
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Contaminantes Atmosféricos/análisis , Contaminación del Aire/prevención & control , Residuos/análisis , Aerosoles/análisis , Electrodos , Tamaño de la Partícula , Suspensiones , Agua/químicaRESUMEN
Porous carbon microsheet anodes with Li-ion storage capacity exceeding the theoretical limit are for the first time derived from waste packing-peanuts. Crystallinity, surface area, and porosity of these 1 µm thick carbon sheets were tuned by varying the processing temperature. Anodes composed of the carbon sheets outperformed the electrochemical properties of commercial graphitic anode in Li-ion batteries. At a current density of 0.1 C, carbon microsheet anodes exhibited a specific capacity of 420 mAh/g, which is slightly higher than the theoretical capacity of graphite (372 mAh/g) in Li-ion half-cell configurations. At a higher rate of 1 C, carbon sheets retained 4-fold higher specific capacity (220 mAh/g) compared to those of commercial graphitic anode. After 100 charge-discharge cycles at current densities of 0.1 and 0.2 C, optimized carbon sheet anodes retained stable specific capacities of 460 and 370 mAh/g, respectively. Spectroscopic and microscopic investigations proved the structural integrity of these high-performance carbon anodes during numerous charge-discharge cycles. Considerably higher electrochemical performance of the porous carbon microsheets are endorsed to their disorderness that facilitate to store more Li-ions than the theoretical limit, and porous 2-D microstructure enabling fast solid-state Li-ion diffusion and superior interfacial kinetics. The work demonstrated here illustrates an inexpensive and environmentally benign method for the upcycling of packaging materials into functional carbon materials for electrochemical energy storage.
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Carbono/química , Suministros de Energía Eléctrica , Litio/química , Embalaje de Productos , Reciclaje , Técnicas Electroquímicas , Electrodos , Iones/química , Microscopía Electrónica de Rastreo , Espectrometría Raman , Termogravimetría , Difracción de Rayos XRESUMEN
A new ternary amorphous GeSnSe (GSS) nanopowder was effectively synthesized by using ball milling under inert atmosphere. Its topographical, microstructural and elemental characterizations revealed the formation of nanoparticles with undefined shape, short-range order and the tailored stoichiometry. Remarkably, this novel amorphous material demonstrates its competences as a promising Li-ion host anode, exhibiting a high cycle performance with a specific charge capacity of 963 mAh g-1 at an applied C-rate of 0.2C with a coulombic efficiency > 99.4 % after 300 cycles. Its high specific capacity, large rate capability, acceptable capacity retention and long cycle life could be attributed to a dual Li-ion storage mechanism that consists mostly of multiple reversible electrochemical processes as conversion and alloying reactions and capacitive processes. Moreover, its stable volume expansion (34 %), moderate electrode polarization (248.9 mV), reasonable charge transfer resistance (83 Ω) and apparent Li-ion diffusion coefficients between 10-9 - 10-14 cm2 s-1 could be promoted by a synergistic effect between Ge (capacity), Sn (conductivity) and Se (stability), which plays an important role on the stability and high cycle performance of the promising GSS-based anode.
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Uniformly mesoporous and thermally robust anatase nanorods were produced with quantitative yield by a simple and efficient one-step approach. The mechanism of this process was revealed by insertion of Eu(3+) cations from the reaction medium as luminescent probes. The obtained structure displays an unusually high porosity, an active surface area of about 300 m(2) g(-1) and a specific capacity of 167 mA h g(-1) at a C/3 rate, making it attractive as an anode electrode for Li-ion batteries. An additional attractive feature is its remarkable thermal stability; heating to 400 °C results in a decrease in the active surface area to a still relatively high value of 110 m(2) g(-1) with conservation of open mesoporosity. Thermal treatment at 800 °C or higher, however, causes transformation into a non-porous rutile monolith, as commonly observed with nanoscale titania.
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Suministros de Energía Eléctrica , Litio/química , Nanotubos/química , Titanio/química , Electrodos , Europio/química , Colorantes Fluorescentes/química , Iones/química , Porosidad , TemperaturaRESUMEN
Ineffectiveness of Li-ion batteries (LIBs) in cold climates hinders electronics to work in various conditions including frigid environments, despite high demands. Given that intrinsic properties of LIB materials cause this problem, optimized cell chemistries ultimately are required for low-temperature usage. In this study, Li-metal batteries (LMBs) composed of a Li-metal anode (LMA) stabilized by a localized high-concentration electrolyte (LHCE) are found to significantly enhance low-temperature performance. The LHCE allows the LMA to have compact and regular deposition and excellent plating/stripping efficiency at sub-zero temperatures. The LHCE produces an inorganic-rich solid-electrolyte interphase with larger amounts of Li2 O/LiF interfaces, dominance of ion aggregates in Li+ solvation, and enhanced Li+ transport, which can greatly improve the LMA stability. LMB full cells based on LiNi0.8 Co0.1 Mn0.1 O2 cathodes with the tailored electrolyte show high retentions of 75 and 64 % at -20 and -40 °C, respectively. Furthermore, the LMB configuration retains its charge-discharge capability even at -60 °C.
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The electrochemical instability of ether-based electrolyte solutions hinders their practical applications in high-voltage Li metal batteries. To circumvent this issue, here, we propose a dilution strategy to lose the Li+/solvent interaction and use the dilute non-aqueous electrolyte solution in high-voltage lithium metal batteries. We demonstrate that in a non-polar dipropyl ether (DPE)-based electrolyte solution with lithium bis(fluorosulfonyl) imide salt, the decomposition order of solvated species can be adjusted to promote the Li+/salt-derived anion clusters decomposition over free ether solvent molecules. This selective mechanism favors the formation of a robust cathode electrolyte interphase (CEI) and a solvent-deficient electric double-layer structure at the positive electrode interface. When the DPE-based electrolyte is tested in combination with a Li metal negative electrode (50 µm thick) and a LiNi0.8Co0.1Mn0.1O2-based positive electrode (3.3 mAh/cm2) in pouch cell configuration at 25 °C, a specific discharge capacity retention of about 74% after 150 cycles (0.33 and 1 mA/cm2 charge and discharge, respectively) is obtained.
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Though layered sodium oxide materials are identified as promising cathodes in sodium-ion batteries, biphasic P3/O3 depicts improved electrochemical performance and structural stability. Herein, a coexistent P3/O3 biphasic cathode material was synthesized with "LiF" integration, verified with X-ray diffraction and Rietveld refinement analysis. Furthermore, the presence of Li and F was deduced by inductively coupled plasma-optical emission spectrometry (ICP-OES) and energy dispersive X-ray spectroscopy (EDS). The biphasic P3/O3 cathode displayed an excellent capacity retention of 85% after 100 cycles (0.2C/30 mA g-1) at room temperature and 94% at -20 °C after 100 cycles (0.1C/15 mA g-1) with superior rate capability as compared to the pristine cathode. Furthermore, a full cell comprising a hard carbon anode and a biphasic cathode with 1 M NaPF6 electrolyte displayed excellent cyclic stabilities at a wider temperature range of -20 to 50 °C (with the energy density of 151.48 Wh kg-1) due to the enhanced structural stability, alleviated Jahn-Teller distortions, and rapid Na+ kinetics facilitating Na+ motion at various temperatures in sodium-ion batteries. The detailed post-characterization studies revealed that the incorporation of LiF accounts for facile Na+ kinetics, boosting the overall Na storage.
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Advanced wave-shape non-graphitizable carbon sheets are derived, comprising mesoporous weaved turbostratic micropore enabled stable Na+ ion storage. The non-graphitizable amorphous characteristics are determined from the obtained two broad diffraction peaks at 22.7° and 43.8°. The observed D-band at 1325 cm-1 and G-band at 1586 cm-1 confirm the disordered graphitic structure, attributed to the measured specific surface area of 54 m2 g-1. Mesoporous weaved wave-shape carbon sheet architecture is confirmed by surface morphological studies, showing lattice fringes of disordered graphitic structures and dispersed ring patterns for the non-crystalline characteristics. The predominant stable redox peak at 0.014 V/0.185 V and the broader rectangular shape between 0.9 and 0.15 V depict the adsorption-micropore filling mechanism. The mesoporous hard carbon sheet delivers discharge-charge capacities of 450/311 mAh g-1 (1st cycle) and 263/267 mAh g-1 (250th cycle) at 25 mA g-1, exhibiting a superior anode for sodium-ion batteries. Besides, in situ multimode calorimetry results disclose that the micropore filling Na+ ion storage shows a higher released total heat energy of 721 J g-1 than the adsorption (471 J g-1). Ultimately, differential scanning calorimetry analysis of micropore filling Na+ ion storage (discharged state at 0.01 V) has revealed a predominant exothermic peak at 156 °C with the highest released total heat energy of 2183 J g-1 compared to adsorption (553 J g-1) and deintercalation (85 J g-1), indicating that micropore filling status is more unsafe than the adsorption and deintercalation for SIBs.
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Ionically conducting, porous separator membranes with submicrometer size pores play an important role in governing the outcome of lithium-ion batteries (LIBs) in terms of life, safety, and effective transport of ions. Though the polyolefin membranes have dominated the commercial segment for the past few decades, to develop next-generation batteries with high-energy density, high capacity, and enhanced safety, there is a need to develop advanced separators with superior thermal stability, electrolyte interfacial capabilities, high melting temperature, and mechanical stability at elevated temperatures. Here, aramid nanofiber separators with enhanced mechanical and thermal stability dried at the critical point are processed and tested for mechanical strength, wettability, electrochemical performance, and thermal safety aspects in LIBs. These separators outperform Celgard polypropylene in all aspects such as delivering a high Young's modulus of 6.9 ± 1.1 GPa, and ultimate tensile strength of 170 ± 25 MPa. At 40 and 25 °C, stable 200 and 300 cycles with 10% and 11% capacity fade were obtained at 1 C rate, respectively. Multimode calorimetry, specially designed to study thermal safety aspects of LIB coin cells, demonstrates low exothermicity for critical-point-dried aramid nanofiber separators, and post-diagnosis illustrates preservation of structural integrity up to 300 °C, depicting possibilities of developing advanced safer, high-performance LIBs.
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Polyimide-Al2O3 membranes are developed as a direct alternative to current polyolefin separators by the electrospinning technique and their chemical structures confirm the carbonyl group with the presence of asymmetric and symmetric stretching and bending vibrations at 1778, 1720, and 720 cm-1 and stretching vibration at 1373 cm-1 for the imide group. Porous nanofiber architecture morphology is realized with a nanofiber thickness of â¼200 nm and shows an ultrasmooth surface and >1 µm pore size in the architecture, built with the chemical constituents of carbon, nitrogen, aluminum, and oxygen elements. The galvanostatic cycling study of the Li/PI-Al2O3/LiFePO4 lithium cell delivers stable charge-discharge capacities of 144/143 mAh g-1 at 0.2 C and 110/100 mAh g-1 at 1 C for 1-100 cycles. The fabricated MCMB/PI-Al2O3/LiFePO4 lithium-ion full-cell reveals less charge transfer resistance of Rct â¼ 25 Ω and yields stable charge-discharge capacities of 125/119 mAh g-1. The thermogravimetric curve for the PI-Al2O3 separator discloses thermal stability up to 525 °C, and the differential scanning calorimetric curve shows a straight line until 300 °C and depicts high thermal stability than the PP separator. In situ multimode calorimetry analysis of the MCMB/PP/LiFePO4 full-cell showed a pronounced exothermic peak at 225 °C with a higher released heat energy of 211 J g-1 at the thermal runaway event, while the MCMB/PI-Al2O3/LiFePO4 full-cell revealed an almost 8-fold less exothermic released heat energy of 25 J g-1 than the Celgard polypropylene separator, which was because the MCMB anode and LiFePO4 cathode can be mechanically isolated without any additional separator's melting and burning reactions, as a fire-suppressant separator for lithium-ion batteries.
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The advent of the COVID-19 pandemic has initiated a radical attention shift of society toward the severe consequences it has had over human health, shadowing a symmetrically, if not more, important issue of the rapid intensification in the amount of plastic waste that has been generated over the due course of time. Such a growth in the plastic footprint across the globe has led to a carbon positive environment with an increased amount of greenhouse gases (GHGs) released due to the processing of the waste plastic. We aim to address and provide our perception to this pressing challenge that can be decoded via the advancement of upcycling technologies, utilized and augmented worldwide. With the establishment of such sustainable policies and strategies, the global plastic footprint can be systematically mitigated, accelerating the world into economic circularity and environmental sustainability.
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Systematic ex-situ X-ray diffraction (XRD) characterization and electrochemical study revealed the key roles that the cut-off voltage and fluoroethylene carbonate (FEC) additive play on improving electrochemical performance of the Bi3Ge4O12-based (BGO) electrode. The ex-situ XRD analysis revealed that BGO particles suffer multiphase transitions during the (dis)charge reactions, being observed some phases as Bi2O2.33, BiLi3, Li2O, Ge4Li15, Ge2Li7, Ge3Li7, Ge5Li22, Ge4Li9, Bi2O3 and GeO2. The electrochemical evaluation exhibited that the addition of 5 v/v% of FEC in 1.0 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate and diethyl carbonate (EC: DEC) at an applied cut-off voltage (1.5 V vs Li/Li+) improves the specific capacity (29%, delivering 479 mAh g-1), capacity retention (12%) and rate capability (369 mAh g-1 at 1000 mA g-1) of the BGO-based electrode. Also, FEC promotes the formation of a stable solid-electrolyte interface (SEI) layer on the anode at a cut-off voltage of 1.5 V vs Li/Li+. It displays the lowest values of SEI and charge transfer (CT) resistances, and electrode polarization, improving the reversibility of the alloying reactions related to Ge-Li and Bi-Li and maintaining their redox activity after 100 cycles, according to dQ dV-1 data.
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1 M LiFSI in cyclopentyl methyl ether is shown as a novel electrolyte with a unique solvation structure to form a thin robust multilayer solid electrolyte interface with an inorganic LiF-rich inner layer. Aggregates and contact ion pairs are actively formed in the solvation shell and reduced on the graphite anode during lithiation. This EC-free electrolyte provides 86.9% initial efficiency, and 355 mA h g-1 over 350 cycles with an excellent capacity retention of 84% at a 1C rate. An excellent low-temperature performance of 370, 337, and 330 mA h g-1 at 0, -10, and -20 °C, respectively, at a 0.1C rate is recorded. Furthermore, at -40 °C, the graphite half-cell has a capacity of 274 mA h g-1 without electrolyte freezing.
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Detection of toxic and flammable gases and volatile organic compounds (VOCs) released from Li-ion batteries during thermal runaway can generate an early warning. A submicron (â¼0.15 µm)-thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) sensor film is coated on a platinum electrode through a facile aqueous dispersion. The resulting sensor reliably detected different volatile organic compounds (VOCs) released during the early stages of thermal runaway of lithium-ion batteries (LIBs) even at low concentrations. The single-electrode sensor utilizes impedance spectroscopy to measure ethyl methyl carbonate and methyl formate concentrations at 5, 15, and 30 ppm independently and in various combinations using ethanol as a reference. In contrast to DC resistance measurement, which provides a single parameter, impedance spectroscopy provides a wealth of information, including impedance and phase angle at multiple frequencies as well as fitted charge transfer resistance and constant-phase elements. Different analytes influence the measurement of different parameters to varying degrees, enabling distinction using a single sensing material. The response time for ethyl methyl carbonate was measured to be 6 s. Three principal components (PCs) preserve more than 95% of information and efficiently enable discrimination of different classes of analytes. Application of low-power PEDOT:PSS-based gas sensors will facilitate cost-effective early detection of VOCs and provide early warning to battery management systems (BMS), potentially mitigating catastrophic thermal runaway events.