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The high theoretical specific energy and environmental friendliness of zinc-air batteries (ZABs) have garnered significant attention. However, the practical application of ZABs requires overcoming the sluggish kinetics associated with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, 3D self-supported nitrogen-doped carbon nanotubes (N-CNTs) arrays encapsulated by CoNi nanoparticles on carbon fiber cloth (CoNi@N-CNTs/CFC) are synthesized as bifunctional catalysts for OER and ORR. The 3D interconnected N-CNTs arrays not only improve the electrical conductivity, the permeation and gas escape capabilities of the electrode, but also enhance the corrosion resistance of CoNi metals. DFT calculations reveal that the co-existence of Co and Ni synergistically reduces the energy barrier for OOH conversion to OH, thereby optimizing the Gibbs free energy of the catalysts. Additionally, analysis of the change in energy barrier during the rate-determining step suggests that the primary catalytic active center is Ni site for OER. As a result, CoNi@N-CNTs/CFC exhibits superior catalytic activity with an overpotential of 240 mV at 10 mA cm-2 toward OER, and the onset potential of 0.92 V for ORR. Moreover, utilization of CoNi@N-CNTs/CFC in liquid and solid-state ZABs exhibited exceptional stability, manifesting a consistent cycling operation lasting for 100 and 15 h, respectively.
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In traditional machine learning (ML)-based material design, the defects of low prediction accuracy, overfitting and low generalization ability are mainly caused by the training of a single ML model. Here, a Soft Voting Ensemble Learning (SVEL) approach is proposed to solve the above issues by integrating multiple ML models in the same scene, thus pursuing more stable and reliable prediction. As a case study, SVEL is applied to develop the broad chemical space of novel pyrochlore electrocatalysts with the molecular formula of A2B2O7, to explore promising pyrochlore oxides and accelerate predictions of unknown pyrochlore in the periodic table. The model successfully established the structure-property relationship of pyrochlore, and selected six cost-effective pyrochlore from the periodic table with a high prediction accuracy of 91.7%, all of which showed good electrocatalytic performance. SVEL not only effectively avoids the high costs of experimentation and lengthy computations, but also addresses biases arising from data scarcity in single models. Furthermore, it has significantly reduced the research cycle of pyrochlore by ≈ 22 years, offering broad prospects for accelerating the development of materials genomics. SVEL method is intended to integrate multiple AI models to provide broader model training clues for the AI material design community.
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Deep-sea equipment usually operates under dwell-fatigue condition, which means the equipped energy storage devices must survive under the changing pressure. Special mechanical designs should be considered to maintain the electrochemical performance of electrodes under this extreme condition. In this work, an effective assembly strategy is proposed to accommodate the dwell-fatigue loading using Ag decorated reduced graphene oxide (rGO) foam (denoted as AGF) as a superelastic and robust Zn host. The wet-press assembly process enables the formation of highly porous and robust framework. The strong synergetic effect between rGO and Ag further guarantees AGF's superelasticity and ultrahigh mechanical strength. Meanwhile, the homogeneously distributed Ag species on the rGO sheets act as zincophilic sites to effectively facilitate Zn plating. Furthermore, AGF offers enough space to address the expansion during the charge and discharge cycles. As expected, the symmetrical cell using this AGF@Zn host demonstrates a long lifespan over 400 h at a depth-of-discharge of 50%. It is worth mentioning that the superelastic AGF host realizes stable Zn plating/stripping under varying pressures.
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High-entropy alloys (HEAs) have attracted considerable attention, owing to their exceptional characteristics and high configurational entropy. Recent findings demonstrated that incorporating HEAs into sulfur cathodes can alleviate the shuttling effect of lithium polysulfides (LiPSs) and accelerate their redox reactions. Herein, we synthesized nano Pt0.25Cu0.25Fe0.15Co0.15Ni0.2 HEAs on hollow carbons (HCs; denoted as HEA/HC) by a facile pyrolysis strategy. The HEA/HC nanostructures were further integrated into hypha carbon nanobelts (HCNBs). The solid-solution phase formed by the uniform mixture of the five metal elements, i.e., Pt0.25Cu0.25Fe0.15Co0.15Ni0.2 HEAs, gave rise to a strong interaction between neighboring atoms in different metals, resulting in their adsorption energy transformation across a wide, multipeak, and nearly continuous spectrum. Meanwhile, the HEAs exhibited numerous active sites on their surface, which is beneficial to catalyzing the cascade conversion of LiPSs. Combining density functional theory (DFT) calculations with detailed experimental investigations, the prepared HEAs bidirectionally catalyze the cascade reactions of LiPSs and boost their conversion reaction rates. S/HEA@HC/HCNB cathodes achieved a low 0.034% decay rate for 2000 cycles at 1.0 C. Notably, the S/HEA@HC/HCNB cathode delivered a high initial areal capacity of 10.2 mAh cm-2 with a sulfur loading of 9 mg cm-2 at 0.1 C. The assembled pouch cell exhibited a capacity of 1077.9 mAh g-1 at the first discharge at 0.1 C. The capacity declined to 71.3% after 43 cycles at 0.1 C. In this work, we propose to utilize HEAs as catalysts not only to improve the cycling stability of lithium-sulfur batteries, but also to promote HEAs in energy storage applications.
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The sluggish reaction kinetics and notorious shuttle effect of polysulfides significantly hinder the practical application of lithium-sulfur batteries (LSBs). Therefore, polysulfides are anchored and their conversion reactions are catalyzed to enhance the performance of LSBs. Herein, an exquisite hierarchical carbon nanoarchitecture decorated with sulfides is designed and introduced into LSBs. Systematic experiments show that the nanoarchitecture not only enables rapid electron/ion migration but also functions as an active catalyst to increase polysulfide conversion, thus effectively reducing the shuttle effect. As a result, LSBs with the nanoarchitecture modified separator exhibited outstanding rate capacity (724.9 mA h g-1 at 5C), low self-discharge capacity loss (4.1% capacity loss after 72 h), and exceptional reversible capacity (1518.3 mA h g-1 at 0.1C and 25.6% capacity loss after 100 cycles). Through the design of a multifunctional separator, this study offers an effective way to minimize the shuttle effect and speed up redox conversion. The strategy of constructing nanoarchitectures provides an innovative route for hierarchical heterocatalyst design for LSBs.
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Lithium-sulfur batteries (LSBs) are considered to be one of the most promising energy storage systems because of the ultrahigh energy density. However, their shuttle effect and slow redox kinetics seriously hinder the development of LSBs. To solve these issues, the perovskite La1-xSrxMnO3-δ (x = 0-0.5) with different oxygen vacancy concentrations were prepared by a facile liquid-phase synthesis and followed by the thermal annealing. The La1-xSrxMnO3-δ can not only anchor lithium polysulfides (LiPSs), but also catalyze the conversion of LiPSs. The detailed kinetic analysis and density functional theory calculations reveal that the optimal level of oxygen vacancies can effectively increase the binding energy between perovskites and LiPSs, and effectively promote the LiPS conversion kinetics. The S/La0.6Sr0.4MnO3-δ cathode with a moderate oxygen vacancy concentration exhibits high rate performance and ultrahigh capacity retention of 93.2% after 150 cycles at 0.1 C, which provides a potential for practical applications of LSBs. This work reveals the application of perovskite materials in the development of advanced LSBs.
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Bifunctional catalysts have inherent advantages in simplifying electrolysis devices and reducing electrolysis costs. Developing efficient and stable bifunctional catalysts is of great significance for industrial hydrogen production. Herein, a bifunctional catalyst, composed of nitrogen and sulfur co-doped carbon-coated trinickel disulfide (Ni3S2)/molybdenum dioxide (MoO2) nanowires (NiMoS@NSC NWs), is developed for seawater electrolysis. The designed NiMoS@NSC exhibited high activity in alkaline electrolyte with only 52 and 191 mV overpotential to attain 10 mA cm-2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Significantly, the electrolyzer (NiMoS@NSC||NiMoS@NSC) based on this bifunctional catalyst drove 100 mA cm-2 at only 1.71 V along with a robust stability over 100 h in alkaline seawater, which is superior to a platinum/nickel-iron layered double hydroxide couple (Pt||NiFe LDH). Theoretical calculations indicated that interfacial interactions between Ni3S2 and MoO2 rearranged the charge at interfaces and endowed Mo sites at the interfaces with Pt-like HER activity, while Ni sites on Ni3S2 surfaces at non-interfaces are the active centers for OER. Meanwhile, theoretical calculations and experimental results also demonstrated that interfacial interactions improved the electrical conductivity, boosting reaction kinetics for both HER and OER. This study presented a novel insight into the design of high-performance bifunctional electrocatalysts for seawater splitting.
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The development of lithium-sulfur batteries (LSBs) is impeded by the shuttle effect of polysulfides (LiPSs) and the sluggish nucleation of Li2S. To address these challenges, incorporating electrocatalysts into sulfur host materials represents an effective strategy for promoting polysulfide conversion, in tandem with the rational design of multifunctional sulfur host materials. In this study, Pt nanoparticles are integrated into biomass-derived carbon materials by solution deposition method. Pt, as an electrocatalyst, not only enhances the electrical conductivity of sulfur cathodes and effectively immobilizes LiPSs but also catalyzes the redox reactions of sulfur species bidirectionally. Additionally, Pt helps regulate the 3D deposition and growth of Li2S while reducing the reaction energy barrier. Consequently, this accelerates the conversion of LiPSs in LSBs. Furthermore, the catalytic ability of Pt for the redox reactions of sulfur species, along with its influence on the 3D deposition and growth of Li2S, is elucidated using electrochemical kinetic analyses and classical models of electrochemical deposition. The cathodes exhibit a high initial specific capacity of 1019.1 mAh g-1 at 1 C and a low decay rate of 0.045% over 1500 cycles. This study presents an effective strategy to regulate Li2S nucleation and enhance the kinetics of polysulfide conversion in LSBs.
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The exploitation of efficient, stable and cheap electrocatalyst for oxygen evolution reaction (OER) is very significant to the development of energy technology. In this study, Fe-based metal-organic frameworks (MIL-53(Fe)) self-supporting electrode with a 3D hierarchical open structure was developed through a semi-sacrificial strategy. The self-supporting electrode exhibits an excellent OER performance with an overpotential of 328 mV at 100 mA cm-2 in 1 M KOH, which is superior than that of IrO2 catalyst. Importantly, the optimized self-supporting electrode could operate at 100 mA cm-2 for 520 h without visible decrease in activity. It was also found that the structure of MIL-53(Fe) was in-situ self-reconstructed into oxyhydroxides during OER process. However, the 3D hierarchical open structure assembled with nano-microstructures kept well, which ensured the long-term stability of our self-supporting electrode for OER. Furthermore, density functional theory (DFT) calculations reveal that the FeOOH with rich oxygen vacancy transformed from MIL-53(Fe) plays a key role for the OER catalytic activity. And, the uninterrupted formation of oxygen vacancy during OER process ensures the continuous OER catalytic activity, which is the original source for the ultra-long stability of the self-supporting electrode toward OER. This work explores the way for the construction of efficient self-supporting oxygen electrodes based on MOFs.
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Lithium-sulfur (Li-S) batteries have been considered one of the most promising candidates for next-generation energy storage devices due to their high theoretical energy density and low cost. Nonetheless, the practical application of Li-S batteries is still inhibited by their lithium polysulfide (LiPS) shuttling and sluggish redox kinetics, which cause rapid capacity decay and inferior rate performance. Hence, anchoring LiPSs and catalyzing their conversion reactions are imperative to enhance the performance of Li-S batteries. In this work, one-dimensional (1D) porous carbon-encapsulated CoS2 (CoS2@C) fiber structures were prepared through a simple two-step hydrothermal reaction and they exhibited a robust LiPS trapping ability and rapid catalytic conversion of LiPSs. The formed three-dimensional (3D) architecture (CoS2@C/MWCNT) facilitates the physical adsorption of LiPSs and rapid ion transport. The electrode exhibited a high initial capacity of 1329.5 mA h g-1 at a current density of 0.1 C and a reversible capacity of 1060.6 mA h g-1 after 100 cycles, with an 80% capacity retention rate. Meanwhile, the decay rate of the electrode is 0.048% per cycle at 1 C and after 500 cycles. With a sulfur loading of 3 mg cm-2, the capacity retention rate is approximately 83.7% after 80 cycles.
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Exploiting dual-functional photoelectrodes to harvest and store solar energy is a challenging but efficient way for achieving renewable energy utilization. Herein, multi-heterostructures consisting of N-doped carbon coated MoS2 nanosheets supported by tubular TiO2 with photoelectric conversion and electronic transfer interfaces are designed. When a photo sodium ion battery (photo-SIB) is assembled based on the heterostructures, its capacity increases to 399.3â mAh g-1 with a high photo-conversion efficiency of 0.71 % switching from dark to visible light at 2.0â A g-1 . Remarkably, the photo-SIB can be recharged by light only, with a striking capacity of 231.4â mAh g-1 . Experimental and theoretical results suggest that the proposed multi-heterostructures can enhance charge transfer kinetics, maintain structural stability, and facilitate the separation of photo-excited carriers. This work presents a new strategy to design dual-functional photoelectrodes for efficient use of solar energy.
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Lithium, with its high theoretical capacity and low potential, has been widely investigated as the anode in energy storage/conversion devices. However, their commercial applications always suffer from undesired dendrite growth, which forms in the charging process and may puncture the separator, leading to short cycle lives and even security problems. Herein, by an in situ displacement reaction using SnF2 at room temperature, we constructed an artificial solid electrolyte interface (ASEI) of LiF/Li-Sn outside the Li anode. This hybrid strategy can induce a synergy between the high Li+ conductivity of the Li-Sn alloy and good electrical insulation of LiF. Moreover, extreme synergy can be achieved by moderating the thickness of the LiF/Li-Sn ASEI, guiding dendrite-free lithium plating and stripping. As a result, a Li//LiFePO4 battery that is assembled from the LiF/Li-Sn ASEI-engineered Li anode can obtain 1000 cycled lives with 86.3% capacity retention under a charge/discharge rate of 5 C. This work provides an alternative way to construct dendrite-free lithium metal anodes, which significantly benefit the cycle lives of LMBs.
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Aqueous Mg-ion batteries (MIBs) lack reliable anode materials. This study concerns the design and synthesis of a new anode material - a π-conjugate of 3D-poly(3,4,9,10-perylenetracarboxylic diimide-1,3,5-triazine-2,4,6-triamine) [3D-P(PDI-T)] - for aqueous MIBs. The increased aromatic structure inhibits solubility in aqueous electrolytes, enhancing its structural stability. The 3D-P(PDI-T) anode exhibits several notable characteristics, including an extremely high rate capacity of 358â mAh g-1 at 0.05â A g-1 , A 3D-P(PDI-T)âMg2 MnO4 full cell exhibits a reversible capacity of 148â mAh g-1 and a long cycle life of 5000â cycles at 0.5â A g-1 . The charge storage mechanism reveals a synergistic interaction of Mg2+ and H+ cations with C-N/C=O groups. The assembled 3D-P(PDI-T)âMg2 MnO4 full cell exhibits a capacity retention of around 95 % after 5000â cycles at 0.5â A g-1 . This 3D-P(PDI-T) anode sustained its framework structure during the charge-discharge cycling of Mg-ion batteries. The reported results provide a strong basis for a cutting-edge molecular engineering technique to afford improved organic materials that facilitate efficient charge-storage behavior of aqueous Mg-ion batteries.
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Hollow carbon spheres are potential candidates for lightweight microwave absorbers. However, the skin effect of pure carbon-based materials frequently induces a terrible impedance mismatching issue. Herein, small-sized NiO/Ni particles with heterojunctions on the N-doped hollow carbon spheres (NHCS@NiO/Ni) are constructed using SiO2 as a sacrificing template. The fabricated NHCS@NiO/Ni displayed excellent microwave absorbability with a minimum reflection loss of -44.04 dB with the matching thickness of 2 mm and a wider efficient absorption bandwidth of 4.38 GHz with the thickness of 1.7 mm, superior to most previously reported hollow absorbers. Experimental results demonstrated that the excellent microwave absorption property of the NHCS@NiO/Ni are attributed to balanced dielectric loss and optimized impedance matching characteristic due to the presence of NiO/Ni heterojunctions. Theoretical calculations suggested that the redistribution of charge at the interfaces and formation of dipoles induced by N dopants and defects are responsible for the enhanced conduction and polarization losses of NHCS@NiO/Ni. The simulations for the surface current and power loss densities reveal that the NHCS@NiO/Ni has- applicable attenuation ability toward microwave under the practical application scenario. This work paves an efficient way for the reasonable design of small-sized particles with well-defined heterojunctions on hollow nanostructures for high-efficiency microwave absorption.
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Lithium (Li) metal has been recognized as the most promising anode material for next-generation rechargeable batteries. However, the practical application of Li anodes is hampered by the growth of Li dendrites. To address this issue, a robust and uniform Sb-based hybrid lithiophilic protective layer is designed and built by a facile in situ surface reaction approach. As evidenced theoretically and experimentally, the as-prepared hybrid protective layer provides outstanding wettability and fast charge-transfer kinetics. Moreover, the lithiophilic Sb embedded in the protective layer provides a rich site for Li nucleation, which effectively reduces the overpotential and induces uniform Li deposition. Consequently, the symmetric cell exhibits a long lifespan of over 1600 h at 1 mA cm-2 and 1 mAh cm-2 with a low voltage polarization. Furthermore, excellent cycling stability is also obtained in Li-S full cells (60% capacity retention in 800 cycles at 1 C) and Li||LFP full cells (74% capacity retention in 500 cycles at 5 C). This work proposed a facile but efficient strategy to stabilize the Li metal anode.
RESUMEN
The Gibbs free energy of hydrogen adsorption at the edge of molybdenum disulfide (MoS2) is close to that of Pt, meaning that MoS2 is the best candidate to replace Pt-based materials. However, easy agglomeration between layers to mask active sites, lack of catalytic activity in the basal planes, and poor electronic conductivity make MoS2 exhibit dissatisfactory hydrogen evolution reaction (HER) catalytic performance. Here, we successfully construct a van der Waals heterostructure stacked alternately with Mo(SSe)2-x and graphene (Mo(SSe)2-x/G) to enhance its catalytic ability. The introduction of Se into MoS2 and the thermal treatment induce the sample to generate more anion vacancies. Theoretical and experimental results demonstrate the constructed van der Waals heterostructure, the introduced Se element, and the increased anion vacancies are in favor of promoting the number of active sites and improving the electronic conductivity of the catalyst. Therefore, Mo(SSe)2-x/G exhibits superior HER catalytic performance (the overpotentials of 137 mV and 136 mV at a current of 10 mA cm-2) and long-term stabilities (>90 h and 140 h at a current density of 20 mA cm-2) in both acidic and alkaline media.
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The lithium sulfur (Li-S) battery is an active research area in the field of energy storage systems, but the shuttle effect is a serious obstacle hindering its application. Herein, a CoSe2/CoO Mott-Schottky catalyst is blended with carbon nanotubes (CNTs) and subsequently coated onto a commercial separator as a modifier, whereby the synergy between the high electrocatalytic activity of the CoSe2/CoO heterostructure and high conductivity of the CNTs selectively mediate the conversion of sulfur species. As a result, a cell with a CoSe2/CoO-CNTs modified separator displays a high initial discharge capacity of 1573 and 910 mAh/g at 0.1 and 2C, respectively. Furthermore, a low decay rate of 0.070% per cycle can be obtained over 500 cycles at 2C. The results of this study suggest that the as-prepared CoSe2/CoO-CNTs is an effective modifier that can improve the performance of Li-S batteries for use in next-generation energy storage systems. This study provides fundamental insights into the rational design of Mott-Schottky catalysts for practical high-performance Li-S batteries.
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Heterostructures with the electric field effect can excite the charge transfer kinetics of materials due to the driving force of the electric field. Herein, we report a new ReS2/Nb2O5 heterostructure of rhenium disulfide coupled to niobium oxide with a mutually compatible band structure and enriched oxygen vacancies. The unique heterostructure can facilitate the redistribution of charges to induce built-in electric fields and microlocalized electric fields. As expected, the ReS2/Nb2O5 heterostructure shows a superior lithium-ion reversible capacity of 805 mAh g-1 after 2400 h at 0.10 A g-1, and 414 mAh g-1 at 2.00 A g-1. In addition, in situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy analysis reveal the phase transition process of the ReS2/Nb2O5 heterostructure during the electrochemical reaction. This provides deeper insights into the construction of high-performance lithium-ion storage materials based on heterostructures with dual-electric field-driven charge transfer.
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The lithium (Li) ion and electron diffusion behaviors across the actual solid electrolyte interphase (SEI) play a critical role in regulating the Li nucleation and growth and improving the performance of lithium-sulfur (Li-S) batteries. To date, a number of researchers have pursued an SEI with high Li-ion conductivity while ignoring the Li dendrite growth caused by electron tunneling in the SEI. Herein, an artificial anti-electron tunneling layer with enriched lithium fluoride (LiF) and sodium fluoride (NaF) nanocrystals is constructed using a facile solution-soaking method. As evidenced theoretically and experimentally, the LiF/NaF artificial SEI exhibits an outstanding electron-blocking capability that can reduce electron tunneling, resulting in dendrite-free and dense Li deposition beneath the SEI, even with an ultrahigh areal capacity. In addition, the artificial anti-electron tunneling layer exhibits improved ionic conductivity and mechanical strength, compared to those of routine SEI. The symmetric cells with protected Li electrodes achieve a stable cycling of 1500 h. The LiF/NaF artificial SEI endows the Li-S full cells with long-term cyclability under conditions of high sulfur loading, lean electrolyte, and limited Li excess. This study provides a perspective on the design of the SEI for highly safe and practical Li-S batteries.
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Lithium metal is considered to be the best candidate for rechargeable batteries due to its unique advantages. But the instability and the uncontrollable dendrites of the lithium metal anode greatly limit its commercialization. In recent years, in order to obtain stable Li metal anodes, various three-dimensional (3D) current collectors have been proposed. However, for traditional 3D current collectors, its advantages in structure still need to be improved. Therefore, the 3D hierarchical Cu@Ag nanostructure consisting of Ag-decorated Cu nanowires grown on Cu foam as a current collector (denoted as 3D HCu@Ag) is well designed and successfully prepared. Cu nanowires were in situ grown on Cu foam to form a 3D hierarchical current collector to further increase the specific surface area and reduce the local current density, thus suppressing the formation of dendrites. Ag nanoparticles were in situ grown on the surface of Cu nanowires by displacement reaction, which can reduce the overpotential of lithium deposition. Under the synergistic effect of optimal structure and Ag surface modification, 3D HCu@Ag exhibits extremely excellent performance. As a result, the Li-3D HCu@Ag symmetrical cell exhibits a lifetime of 1500 h with a very low voltage hysteresis. More importantly, in practical application, the Li-3D HCu@Ag||LFP full cell can cycle stably for 200 cycles at 1C and maintain an extremely high-capacity retention rate of 78.5%. The experiment results show that this design provides a new idea for the lithiophilic 3D current collector for stable lithium metal anode.