Rechargeable lithium metal batteries are next generation energy storage devices with high energy density, but face challenges in achieving high energy density, high safety, and long cycle life. Here, ...lithium metal batteries in a novel nonflammable ionic‐liquid (IL) electrolyte composed of 1‐ethyl‐3‐methylimidazolium (EMIm) cations and high‐concentration bis(fluorosulfonyl)imide (FSI) anions, with sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a key additive are reported. The Na ion participates in the formation of hybrid passivation interphases and contributes to dendrite‐free Li deposition and reversible cathode electrochemistry. The electrolyte of low viscosity allows practically useful cathode mass loading up to ≈16 mg cm−2. Li anodes paired with lithium cobalt oxide (LiCoO2) and lithium nickel cobalt manganese oxide (LiNi0.8Co0.1Mn0.1O2, NCM 811) cathodes exhibit 99.6–99.9% Coulombic efficiencies, high discharge voltages up to 4.4 V, high specific capacity and energy density up to ≈199 mAh g−1 and ≈765 Wh kg−1 respectively, with impressive cycling performances over up to 1200 cycles. Highly stable passivation interphases formed on both electrodes in the novel IL electrolyte are the key to highly reversible lithium metal batteries, especially for Li–NMC 811 full batteries.
A nonflammable ionic‐liquid electrolyte is developed for high‐safety and high‐energy‐density Li metal batteries, allowing practically useful cathode mass loading up to 16 mg cm−2, realizing high specific capacity and energy density (199 mAh g−1 and 765 Wh kg−1) with impressive cycling performances. The robust passivation interphases formed on both electrodes are key to realizing impressive battery performances.
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Rechargeable sodium metal batteries with high energy density could be important to a wide range of energy applications in modern society. The pursuit of higher energy density should ideally come with ...high safety, a goal difficult for electrolytes based on organic solvents. Here we report a chloroaluminate ionic liquid electrolyte comprised of aluminium chloride/1-methyl-3-ethylimidazolium chloride/sodium chloride ionic liquid spiked with two important additives, ethylaluminum dichloride and 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide. This leads to the first chloroaluminate based ionic liquid electrolyte for rechargeable sodium metal battery. The obtained batteries reached voltages up to ~ 4 V, high Coulombic efficiency up to 99.9%, and high energy and power density of ~ 420 Wh kg
and ~ 1766 W kg
, respectively. The batteries retained over 90% of the original capacity after 700 cycles, suggesting an effective approach to sodium metal batteries with high energy/high power density, long cycle life and high safety.
•A brief summary of challenges and underlying opportunities was expressed.•This paper highlights issues related to employ liquid electrolytes in ZABs.•Various suggestions to reduce dendrites ...formation and ZnO layer was presented.•Additives demonstrate as promising approach for liquid and polymer electrolytes.
In the past few years, there has been a growing level of interest in the research and development of energy storage systems such as batteries. This is a direct consequence of the soaring rise in global energy demand across various commercial and industrial sectors. Lithium ion batteries have set out a feasible horizon for widespread deployment as small-scale energy storage devices due to their high efficiency and cyclability. However, the availability and cost of lithium have limited the commercial deployment of large-scale systems. On the other hand, zinc-air batteries have demonstrated comparable efficiencies and have been reported to be suitable replacements for lithium batteries in large-scale applications. Nevertheless, more research has been undertaken to address the issues associated with the cycling processes of these batteries. Secondary zinc-air batteries are yet to be commercially proven feasible due to the low charge/discharge cycle life of electrodes. The main problems of secondary alkaline zinc–air batteries are dendritic growth resulting in an alternation of morphology and structure, self-dissolutionand the consequent occurrence of hydrogen evolution reactions. However, by and large, inefficient electrolytes are the main culprits responsible for the reduced performance of zinc-air batteries. Therefore, a comprehensive review of current advancements in the development of suitable electrolytes to promote zinc-air batteries towards commercial application will provide a perspective for future rechargeable zinc-air batteries. In this in-depth review, the effects of the types of electrolytes and their properties on the electrochemical performance of Zn anode have been discussed. A demonstration of the current research status and challenges set upon the large-scale deployment of zinc-air batteries will facilitate the educated steering of future research directions in this critically important realm.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Anode‐free lithium‐metal batteries employ in situ lithium‐plated current collectors as negative electrodes to afford optimal mass and volumetric energy densities. The main challenges to such ...batteries include their poor cycling stability and the safety issues of the flammable organic electrolytes. Here, a high‐voltage 4.7 V anode‐free lithium‐metal battery is reported, which uses a Cu foil coated with a layer (≈950 nm) of silicon–polyacrylonitrile (Si‐PAN, 25.5 µg cm−2) as the negative electrode, a high‐voltage cobalt‐free LiNi0.5Mn1.5O4 (LNMO) as the positive electrode and a safe, nonflammable ionic liquid electrolyte composed of 4.5 m lithium bis(fluorosulfonyl)imide (LiFSI) salt in N‐methyl‐N‐propyl pyrrolidiniumbis(fluorosulfonyl)imide (Py13FSI) with 1 wt% lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as additive. The Si‐PAN coating is found to seed the growth of lithium during charging, and reversibly expand/shrink during lithium plating/stripping over battery cycling. The wide‐voltage‐window electrolyte containing a high concentration of FSI− and TFSI− facilitates the formation of stable solid‐electrolyte interphase, affording a 4.7 V anode‐free Cu@Si‐PAN/LiNi0.5Mn1.5O4 battery with a reversible specific capacity of ≈120 mAh g−1 and high cycling stability (80% capacity retention after 120 cycles). These results represent the first anode‐free Li battery with a high 4.7 V discharge voltage and high safety.
4.7 V Cu@Si‐PAN/LiNi0.5Mn1.5O4 anode‐free Li batteries with a reversible specific capacity of ≈120 mAh g−1 and high capacity retention of 80% after 120 cycles are reported. With the nonflammable F‐rich ionic liquid electrolyte and the seeding Si‐PAN layer (950 nm), an enhanced safety and high‐voltage anode‐free Li battery without dendritic Li growth is demonstrated.
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5.
Rechargeable Li/Cl2 Battery Down to −80 °C Liang, Peng; Zhu, Guanzhou; Huang, Cheng‐Liang ...
Advanced materials (Weinheim),
02/2024, Volume:
36, Issue:
7
Journal Article
Peer reviewed
Low temperature rechargeable batteries are important to life in cold climates, polar/deep‐sea expeditions, and space explorations. Here, this work reports 3.5–4 V rechargeable lithium/chlorine ...(Li/Cl2) batteries operating down to −80 °C, employing Li metal negative electrode, a novel carbon dioxide (CO2) activated porous carbon (KJCO2) as the positive electrode, and a high ionic conductivity (≈5–20 mS cm−1 from −80 °C to room‐temperature) electrolyte comprised of aluminum chloride (AlCl3), lithium chloride (LiCl), and lithium bis(fluorosulfonyl)imide (LiFSI) in low‐melting‐point (−104.5 °C) thionyl chloride (SOCl2). Between room‐temperature and −80 °C, the Li/Cl2 battery delivers up to ≈29 100–4500 mAh g−1 first discharge capacity (based on carbon mass) and a 1200–5000 mAh g−1 reversible capacity over up to 130 charge–discharge cycles. Mass spectrometry and X‐ray photoelectron spectroscopy probe Cl2 trapped in the porous carbon upon LiCl electro‐oxidation during charging. At −80 °C, Cl2/SCl2/S2Cl2 generated by electro‐oxidation in the charging step are trapped in porous KJCO2 carbon, allowing for reversible reduction to afford a high discharge voltage plateau near ≈4 V with up to ≈1000 mAh g−1 capacity for SCl2/S2Cl2 reduction and up to ≈4000 mAh g−1 capacity at ≈3.1 V plateau for Cl2 reduction.
This work reports a −80 °C ≈4.0 V rechargeable lithium/chlorine battery with a 1200–5000 mAh g−1 reversible capacity over up to 130 cycles, employing the newly engineered porous carbon cathode and SOCl2‐based electrolyte. X‐ray spectroscopy and mass spectrometry reveal the highly reversible LiCl/Cl2 redox reactions and trapping mechanism of reactive species at −40 °C to −80 °C.
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Graphene is expected to enable superior corrosion protection due to its impermeability and chemical inertness. Previous reports, however, demonstrate limited corrosion inhibition and even corrosion ...enhancement of graphene on metal surfaces. To enable the reliable and complete passivation, the origin of the low inhibition efficiency of graphene was investigated. Combining electrochemical and morphological characterization techniques, nanometer-sized structural defects in chemical vapor deposition grown graphene were found to be the cause for the limited passivation effect. Extremely fast mass transport on the order of meters per second both across and parallel to graphene layers results in an inhibition efficiency of only ∼50% for Cu covered with up to three graphene layers. Through selective passivation of the defects by atomic layer deposition (ALD) an enhanced corrosion protection of more than 99% was achieved, which compares favorably with commercial corrosion protection methods.
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•The novel CNT-CoFe/NC and CNT-CoS2 Fe/NC was fabricated by thermal treatments and vulcanization.•CNT-CoFe/NC shows a better ORR performance than Pt/C while CNT-CoS2 Fe/NC shows a ...better OER performance than RuO2.•The hybrid catalysts, CNT-CoFe/NC + CNT-CoS2 Fe/NC, demonstrate a superior performance of rechargeable Zn-air battery.
Catalysts with embedded and functionalized elements used for the effective control of oxygen-reduction (ORRs) and oxygen-evolution reactions (OERs) are the key to developing high-performance rechargeable Zn–air batteries (ZABs). Here, carbon nanotube-grafted, Co–Fe embedded, nitrogen-doped porous carbon nano-frameworks (CNT–Co–Fe/NC) were synthesized through the carbonization of Fe-doped zeolitic imidazolate frameworks and vulcanization of the CNT–Co–Fe/NC to form CNT–CoS2–Fe/NC. The CNT–CoS2–Fe/NC exhibited a superior OER performance with an overpotential of only 1.637 mV at a current density of 10 mA/cm2 and a Tafel slope of 197 mV/dec (which, for RuO2, is 112 mV/dec), whereas the CNT–Co–Fe/NC showed an excellent ORR performance with a Tafel slope of 71 mV/dec (which, for 20 wt% Pt/C, is 91 mV/dec). A ZAB was developed with a hybrid catalyst of 50 wt% CNT–Co–Fe/NC and 50 wt% CNT–CoS2–Fe/NC in the cathode, and it achieved an excellent specific discharge capacity of 814 mAh/g at 50 mA/cm2, high power density of 245 mW/cm2, and outstanding cycle stability of over 1800 cycles (300 h) at 10 mA/cm2 with a very high retention of 95% and small potential gap of 0.68 V, compared to the corresponding values of 803.7 mAh/g, 215.3 mW/cm2, 900 cycles: retention 92%, and potential gap 0.837 V for 150 h for the ZAB with a hybrid catalyst of Pt/C + RuO2. It is hypothesized that the ZAB with the novel hybrid catalyst exhibits its excellent catalytic activity and durability as a result of the synergistic effect of the catalyst’s embedded heteroatoms and nitrogen–metal/carbon framework that enhances the ORR/OER performance, porous carbon nano-framework that enables rapid diffusion and electrical conduction, and carbon nanotubes that complete the external electrical connection between the catalysts.
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High-purity single crystal ZnO nanowires were synthesized by the thermal decomposition of zinc acetate dihydrate at 300°C in air for 3h without a catalyst. The zinc acetate dihydrate was ...characterized by thermogravimetric-differential scanning calorimetry and mass spectrometry (TG–DSC–MS) to determine the thermal decomposition and crystallization temperature. Results reveal that the ZnO nanowires were produced through a dehydration, vaporization/decomposition, and deposition/formation process, which differs from the common vapor–liquid–solid (VLS) mechanism. X-ray diffraction demonstrates that the ZnO nanowires have a wurtzite crystal structure, and scanning electron microscopy shows their diameter and length to be about 40nm and a few micrometers, respectively. High-resolution transmission electron microscopy reveals that the nanowires are of a single crystal, which grew in the 001 direction. In addition, photoluminescence spectra results of the as-grown ZnO nanowires suggest possible applications in ultraviolet emission devices.
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Solar power has rapidly become an increasingly important energy source in many countries over recent years; however, the intermittent nature of photovoltaic (PV) power generation has a significant ...impact on existing power systems. To reduce this uncertainty and maintain system security, precise solar power forecasting methods are required. This study summarizes and compares various PV power forecasting approaches, including time-series statistical methods, physical methods, ensemble methods, and machine and deep learning methods, the last of which there is a particular focus. In addition, various optimization algorithms for model parameters are summarized, the crucial factors that influence PV power forecasts are investigated, and input selection for PV power generation forecasting models are discussed. Probabilistic forecasting is expected to play a key role in the PV power forecasting required to meet the challenges faced by modern grid systems, and so this study provides a comparative analysis of existing deterministic and probabilistic forecasting models. Additionally, the importance of data processing techniques that enhance forecasting performance are highlighted. In comparison with the extant literature, this paper addresses more of the issues concerning the application of deep and machine learning to PV power forecasting. Based on the survey results, a complete and comprehensive solar power forecasting process must include data processing and feature extraction capabilities, a powerful deep learning structure for training, and a method to evaluate the uncertainty in its predictions.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Ti, V, Cr, Mn, Co, and Cu, have been investigated as a third dopant in NiFe sulfide for enhanced oxygen evolution reaction (OER)/oxygen reduction reaction (ORR). The effects of dopant on surface ...electronic structure, conductivity, and thermodynamic barrier of reaction are addressed and discussed. For the OER, X‐ray photoelectron spectroscopy analysis shows that electron transferring from the Ni to the dopants enhances the catalytic performance of the sulfide. Cu doped NiFe sulfide exhibits the best OER performance. For the ORR, density functional theory calculation indicates that Ti, V, Mn, Co, and Cu upshift the d‐band center (ɛd), while Cr downshifts the ɛd. Among the dopants, V leads to optimized electronic structure modification, giving optimized adsorption energy of *O on the Ni, the lowest rate determining step ΔG1, and the best ORR activity. By considering E10‐E1/2 together with the maximum current density of the OER and limited diffusion current density of the ORR, NiFeVS exhibits the best OER/ORR bifunctionality. The performance of NiFeVS as a cathodic catalyst has also been evaluated in a zinc air battery, demonstrating a specific capacity of 698 mAh g−1, maximum power density of 190 mW cm−2, and a superior cycle stability of 2400 cycles (400 h).
Third metal dopant effectively promotes the formation of Ni3+ active site during OER, overcomes the thermodynamic barrier ΔG1 of ORR, and improving the conductivity. The V dopant gives optimized bifunctional OER/ORR electrocatalyst activity having ΔE of 0.765 V and superior cycle stability up to 2400 cycles or 400 h in Zn‐air battery cell.
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