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1.
Active crystal facets can generate special properties for various applications. Herein, we report a (001) faceted nanosheet-constructed hierarchically porous TiO2/rGO hybrid architecture with unprecedented and highly stable lithium storage performance. Density functional theory calculations show that the (001) faceted TiO2 nanosheets enable enhanced reaction kinetics by reinforcing their contact with the electrolyte and shortening the path length of Li+ diffusion and insertion-extraction. The reduced graphene oxide (rGO) nanosheets in this TiO2/rGO hybrid largely improve charge transport, while the porous hierarchy at different length scales favors continuous electrolyte permeation and accommodates volume change. This hierarchically porous TiO2/rGO hybrid anode material demonstrates an excellent reversible capacity of 250 mAh g–1 at 1 C (1 C = 335 mA g–1) at a voltage window of 1.0–3.0 V. Even after 1000 cycles at 5 C and 500 cycles at 10 C, the anode retains exceptional and stable capacities of 176 and 160 mAh g–1, respectively. Moreover, the formed Li2Ti2O4 nanodots facilitate reversed Li+ insertion-extraction during the cycling process. The above results indicate the best performance of TiO2-based materials as anodes for lithium-ion batteries reported in the literature.  相似文献   

2.
Designing new cathodes with high capacity and moderate potential is the key to breaking the energy density ceiling imposed by current intercalation chemistry on rechargeable batteries. The carbonaceous materials provide high capacities but their low potentials limit their application to anodes. Here, we show that Fermi level tuning by p-type doping can be an effective way of dramatically raising electrode potential. We demonstrate that Li(Na)BCF2/Li(Na)B2C2F2 exhibit such change in Fermi level, enabling them to accommodate Li+(Na+) with capacities of 290–400 (250–320) mAh g−1 at potentials of 3.4–3.7 (2.7–2.9) V, delivering ultrahigh energy densities of 1000–1500 Wh kg−1. This work presents a new strategy in tuning electrode potential through electronic band structure engineering.  相似文献   

3.
Microparticulate silicon (Si), normally shelled with carbons, features higher tap density and less interfacial side reactions compared to its nanosized counterpart, showing great potential to be applied as high-energy lithium-ion battery anodes. However, localized high stress generated during fabrication and particularly, under operating, could induce cracking of carbon shells and release pulverized nanoparticles, significantly deteriorating its electrochemical performance. Here we design a strong yet ductile carbon cage from an easily processing capillary shrinkage of graphene hydrogel followed by precise tailoring of inner voids. Such a structure, analog to the stable structure of plant cells, presents ‘imperfection-tolerance’ to volume variation of irregular Si microparticles, maintaining the electrode integrity over 1000 cycles with Coulombic efficiency over 99.5%. This design enables the use of a dense and thick (3 mAh cm–2) microparticulate Si anode with an ultra-high volumetric energy density of 1048 Wh L–1 achieved at pouch full-cell level coupled with a LiNi0.8Co0.1Mn0.1O2 cathode.  相似文献   

4.
The rapid development of printed and microscale electronics imminently requires compatible micro-batteries (MBs) with high performance, applicable scalability, and exceptional safety, but faces great challenges from the ever-reported stacked geometry. Herein the first printed planar prototype of aqueous-based, high-safety Zn//MnO2 MBs, with outstanding performance, aesthetic diversity, flexibility and modularization, is demonstrated, based on interdigital patterns of Zn ink as anode and MnO2 ink as cathode, with high-conducting graphene ink as a metal-free current collector, fabricated by an industrially scalable screen-printing technique. The planar separator-free Zn//MnO2 MBs, tested in neutral aqueous electrolyte, deliver a high volumetric capacity of 19.3 mAh/cm3 (corresponding to 393 mAh/g) at 7.5 mA/cm3, and notable volumetric energy density of 17.3 mWh/cm3, outperforming lithium thin-film batteries (≤10 mWh/cm3). Furthermore, our Zn//MnO2 MBs present long-term cyclability having a high capacity retention of 83.9% after 1300 cycles at 5 C, which is superior to stacked Zn//MnO2 batteries previously reported. Also, Zn//MnO2 planar MBs exhibit exceptional flexibility without observable capacity decay under serious deformation, and remarkably serial and parallel integration of constructing bipolar cells with high voltage and capacity output. Therefore, low-cost, environmentally benign Zn//MnO2 MBs with in-plane geometry possess huge potential as high-energy, safe, scalable and flexible microscale power sources for direction integration with printed electronics.  相似文献   

5.
Understanding the correlation between exposed surfaces and performances of controlled nanocatalysts can aid effective strategies to enhance electrocatalysis, but this is as yet unexplored for the nitrogen reduction reaction (NRR). Here, we first report controlled synthesis of well-defined Pt3Fe nanocrystals with tunable morphologies (nanocube, nanorod and nanowire) as ideal model electrocatalysts for investigating the NRR on different exposed facets. The detailed electrocatalytic studies reveal that the Pt3Fe nanocrystals exhibit shape-dependent NRR electrocatalysis. The optimized Pt3Fe nanowires bounded with high-index facets exhibit excellent selectivity (no N2H4 is detected), high activity with NH3 yield of 18.3 μg h−1 mg−1cat (0.52 μg h−1 cm−2ECSA; ECSA: electrochemical active surface area) and Faraday efficiency of 7.3% at −0.05 V versus reversible hydrogen electrode, outperforming the {200} facet-enclosed Pt3Fe nanocubes and {111} facet-enclosed Pt3Fe nanorods. They also show good stability with negligible activity change after five cycles. Density functional theory calculations reveal that, with high-indexed facet engineering, the Fe-3d band is an efficient d-d coupling correlation center for boosting the Pt 5d-electronic exchange and transfer activities towards the NRR.  相似文献   

6.
As a promising low-cost energy storage device, the development of a rechargeable potassium-ion battery (KIB) is severely hindered by the limited capacity of cathode candidates. Regarded as an attractive capacity-boosting strategy, triggering the O-related anionic redox activity has not been achieved within a sealed KIB system. Herein, in contrast to the typical gaseous open K-O2 battery (O2/KO2 redox), we originally realize the reversible superoxide/peroxide (KO2/K2O2) interconversion on a KO2-based cathode. Controlled within a sealed cell environment, the irreversible O2 evolution and electrolyte decomposition (induced by superoxide anion (O2−) formation) are effectively restrained. Rationally controlling the reversible depth-of-charge at 300 mAh/g (based on the mass of KO2), no obvious cell degradation can be observed during 900 cycles. Moreover, benefitting from electrolyte modification, the KO2-based cathode is coupled with a limited amount of K-metal anode (merely 2.5 times excess), harvesting a K-metal full-cell with high energy efficiency (∼90%) and long-term cycling stability (over 300 cycles).  相似文献   

7.
A high power density and long-lasting stable/disposable magnesium battery anode was explored for a paper-based fluidic battery to power on-chip functions of various Point of Care (POC) devices. The single galvanic cell with magnesium foil anode and silver foil cathode in Origami cellulose chip provided open circuit potential, 2.2 V, and power density, 3.0 mW/cm2. A paper-based fluidic galvanic cell was operated with one drop of water (80 μl) and continued to run until it was dry. To prove the concept about powering on-chip POC devices, two-serial galvanic cells are developed and incorporated with a UV-light emitting diode (λ = 365 nm) and fluorescence assay for alkaline phosphatase reaction. Further, detection using smart phones was performed for quantitative measurement of fluorescent density. To conclude, a magnesium-based fluidic battery paper chip was extremely low-cost, required minute sample volumes, was easy to dispose of, light weight, easy to stack, store and transport, easy to fabricate, scalable, and has faster analysis times.  相似文献   

8.
Contact interface properties are important in determining the performances of devices that are based on atomically thin two-dimensional (2D) materials, especially for those with short channels. Understanding the contact interface is therefore important to design better devices. Herein, we use scanning transmission electron microscopy, electron energy loss spectroscopy, and first-principles calculations to reveal the electronic structures within the metallic (1T′)-semiconducting (2H) MoTe2 coplanar phase boundary across a wide spectral range and correlate its properties to atomic structures. We find that the 2H-MoTe2 excitonic peaks cross the phase boundary into the 1T′ phase within a range of approximately 150 nm. The 1T′-MoTe2 crystal field can penetrate the boundary and extend into the 2H phase by approximately two unit-cells. The plasmonic oscillations exhibit strong angle dependence, that is a red-shift of π+σ (approximately 0.3–1.2 eV) occurs within 4 nm at 1T′/2H-MoTe2 boundaries with large tilt angles, but there is no shift at zero-tilted boundaries. These atomic-scale measurements reveal the structure–property relationships of the 1T′/2H-MoTe2 boundary, providing useful information for phase boundary engineering and device development based on 2D materials.  相似文献   

9.
Many optimization strategies have been employed to stabilize zinc anodes of zinc-ion batteries (ZIBs). Although these commonly used strategies can improve anode performance, they simultaneously induce specific issues. In this study, through the combination of structural design, interface modification, and electrolyte optimization, an ‘all-in-one’ (AIO) electrode was developed. Compared to the three-dimensional (3D) anode in routine liquid electrolytes, the new AIO electrode can greatly suppress gas evolution and the occurrence of side reactions induced by active water molecules, while retaining the merits of a 3D anode. Moreover, the integrated AIO strategy achieves a sufficient electrode/electrolyte interface contact area, so that the electrode can promote electron/ion transfer, and ensure a fast and complete redox reaction. As a result, it achieves excellent shelving-restoring ability (60 hours, four times) and 1200 cycles of long-term stability without apparent polarization. When paired with two common cathode materials used in ZIBs (α-MnO2 and NH4V4O10), full batteries with the AIO electrode demonstrate high capacity and good stability. The strategy of the ‘all-in-one’ architectural design is enlightened to solve the issues of zinc anodes in advanced Zn-based batteries.  相似文献   

10.
Because of their low cost, natural abundance, environmental benignity, plentiful polymorphs, good chemical stability and excellent optical properties, TiO2 materials are of great importance in the areas of physics, chemistry and material science. Much effort has been devoted to the synthesis of TiO2 nanomaterials for various applications. Among them, mesoporous TiO2 materials, especially with hierarchically porous structures, show great potential owing to their extraordinarily high surface areas, large pore volumes, tunable pore structures and morphologies, and nanoscale effects. This review aims to provide an overview of the synthesis and applications of hierarchically mesoporous TiO2 materials. In the first section, the general synthetic strategies for hierarchically mesoporous TiO2 materials are reviewed. After that, we summarize the architectures of hierarchically mesoporous TiO2 materials, including nanofibers, nanosheets, microparticles, films, spheres, core-shell and multi-level structures. At the same time, the corresponding mechanisms and the key factors for the controllable synthesis are highlighted. Following this, the applications of hierarchically mesoporous TiO2 materials in terms of energy storage and environmental protection, including photocatalytic degradation of pollutants, photocatalytic fuel generation, photoelectrochemical water splitting, catalyst support, lithium-ion batteries and sodium-ion batteries, are discussed. Finally, we outline the challenges and future directions of research and development in this area.  相似文献   

11.
Inspired by nature, improving photosensitization represents a vital direction for the development of artificial photosynthesis. The sensitization ability of photosensitizers (PSs) reflects in their electron-transfer ability, which highly depends on their excited-state lifetime and redox potential. Herein, for the first time, we put forward a facile strategy to improve sensitizing ability via finely tuning the excited state of Ru(II)-PSs (Ru-1–Ru-4) for efficient CO2 reduction. Remarkably, [Ru(Phen)2(3-pyrenylPhen)]2+ (Ru-3) exhibits the best sensitizing ability among Ru-1–Ru-4, over 17 times higher than that of typical Ru(Phen)32+. It can efficiently sensitize a dinuclear cobalt catalyst for CO2-to-CO conversion with a maximum turnover number of 66 480. Systematic investigations demonstrate that its long-lived excited state and suitable redox driving force greatly contributed to this superior sensitizing ability. This work provides a new insight into dramatically boosting photocatalytic CO2 reduction via improving photosensitization.  相似文献   

12.
伴随着新能源汽车对动力电池能量密度要求的提高,动力电池的研究变得尤其重要。基于动力电池产业链,通过专利视角分析动力电池产业的发展,从锂离子动力电池产业链上游中的关键材料出发,对锂离子动力电池的正负极材料、隔膜及电解液的发展趋势进行了研究。发展正极材料是大幅度提升动力电池比能量的首选,其将朝着高电压、高容量的方向发展；发展硅基负极材料成为行业共识。接着结合动力电池产业链中下游的关键技术,对动力电池匹配与优化、电池制造工艺及电池回收与梯级利用给出了改进的建议。  相似文献   

13.
Photocatalytic CO2 reduction into energy carriers is of utmost importance due to the rising concentrations of CO2 and the depleting energy resource. However, the highly selective generation of desirable hydrocarbon fuel, such as methane (CH4), from CO2 remains extremely challenging. Herein, we present two stable polyoxometalate-grafted metalloporphyrin coordination frameworks (POMCFs), which are constructed with reductive Zn-ϵ-Keggin clusters and photosensitive tetrakis(4-carboxylphenyl)porphyrin (H2TCPP) linkers, exhibiting high selectivity (>96%) for CH4 formation in a photocatalytic CO2-reduction system. To our knowledge, the high CH4 selectivity of POMCFs has surpassed all of the reported coordination-framework-based heterogeneous photocatalysts for CO2-to-CH4 conversion. Significantly, the introduction of a Zn-ϵ-keggin cluster with strong reducing ability is the important origin for POMCFs to obtain high photocatalytic selectivity for CH4 formation, considering that eight MoV atoms can theoretically donate eight electrons to fulfill the multielectron reduction process of CO2-to-CH4 transformation.  相似文献   

14.
Sodium-based dual-ion batteries (Na-DIBs) show a promising potential for large-scale energy storage applications due to the merits of environmental friendliness and low cost. However, Na-DIBs are generally subject to poor rate capability and cycling stability for the lack of suitable anodes to accommodate large Na+ ions. Herein, we propose a molecular grafting strategy to in situ synthesize tin pyrophosphate nanodots implanted in N-doped carbon matrix (SnP2O7@N-C), which exhibits a high fraction of active SnP2O7 up to 95.6 wt% and a low content of N-doped carbon (4.4 wt%) as the conductive framework. As a result, this anode delivers a high specific capacity ∼400 mAh g−1 at 0.1 A g−1, excellent rate capability up to 5.0 A g−1 and excellent cycling stability with a capacity retention of 92% after 1200 cycles under a current density of 1.5 A g−1. Further, pairing this anode with an environmentally friendly KS6 graphite cathode yields a SnP2O7@N-C||KS6 Na-DIB, exhibiting an excellent rate capability up to 30 C, good fast-charge/slow-discharge performance and long-term cycling life with a capacity retention of ∼96% after 1000 cycles at 20 C. This study provides a feasible strategy to develop high-performance anodes with high-fraction active materials for Na-based energy storage applications.  相似文献   

15.
Outgassing of carbon dioxide from the Earth''s interior regulates the surface climate through deep time. Here we examine the role of cratonic destruction in mantle CO2 outgassing via collating and presenting new data for Paleozoic kimberlites, Mesozoic basaltic rocks and their mantle xenoliths from the eastern North China Craton (NCC), which underwent extensive destruction in the early Cretaceous. High Ca/Al and low Ti/Eu and δ26Mg are widely observed in lamprophyres and mantle xenoliths, which demonstrates that the cratonic lithospheric mantle (CLM) was pervasively metasomatized by recycled carbonates. Raman analysis of bubble-bearing melt inclusions shows that redox melting of the C-rich CLM produced carbonated silicate melts with high CO2 content. The enormous quantities of CO2 in these magmas, together with substantial CO2 degassing from the carbonated melt–CLM reaction and crustal heating, indicate that destruction of the eastern NCC resulted in rapid and extensive mantle CO2 emission, which partly contributed to the early Cretaceous greenhouse climate episode.  相似文献   

16.
Retrieving historical fine particulate matter (PM2.5) data is key for evaluating the long-term impacts of PM2.5 on the environment, human health and climate change. Satellite-based aerosol optical depth has been used to estimate PM2.5, but estimations have largely been undermined by massive missing values, low sampling frequency and weak predictive capability. Here, using a novel feature engineering approach to incorporate spatial effects from meteorological data, we developed a robust LightGBM model that predicts PM2.5 at an unprecedented predictive capacity on hourly (R2 = 0.75), daily (R2 = 0.84), monthly (R2 = 0.88) and annual (R2 = 0.87) timescales. By taking advantage of spatial features, our model can also construct hourly gridded networks of PM2.5. This capability would be further enhanced if meteorological observations from regional stations were incorporated. Our results show that this model has great potential in reconstructing historical PM2.5 datasets and real-time gridded networks at high spatial-temporal resolutions. The resulting datasets can be assimilated into models to produce long-term re-analysis that incorporates interactions between aerosols and physical processes.  相似文献   

17.
Designing highly active nanozymes for various enzymatic reactions remains a challenge in practical applications and fundamental research. In this work, by studying the catalytic functions of natural NADH oxidase (NOX), we devised and synthesized a porous carbon-supported cobalt catalyst (Co/C) to mimic NOX. The Co/C can catalyze dehydrogenation of NADH and transfers electrons to O2 to produce H2O2. Density functional theory calculations reveal that the Co/C can catalyze O2 reduction to H2O2 or H2O considerably. The Co/C can also mediate electron transfer from NADH to heme protein cytochrome c, thereby exhibiting cytochrome c reductase-like activity. The Co/C nanoparticles can deplete NADH in cancer cells, induce increase of the reactive oxygen species, lead to impairment of oxidative phosphorylation and decrease in mitochondrial membrane potential, and cause ATP production to be damaged. This ‘domino effect’ facilitates the cell to approach apoptosis.  相似文献   

18.
Mechanically exfoliated two-dimensional ferromagnetic materials (2D FMs) possess long-range ferromagnetic order and topologically nontrivial skyrmions in few layers. However, because of the dimensionality effect, such few-layer systems usually exhibit much lower Curie temperature (TC) compared to their bulk counterparts. It is therefore of great interest to explore effective approaches to enhance their TC, particularly in wafer-scale for practical applications. Here, we report an interfacial proximity-induced high-TC 2D FM Fe3GeTe2 (FGT) via A-type antiferromagnetic material CrSb (CS) which strongly couples to FGT. A superlattice structure of (FGT/CS)n, where n stands for the period of FGT/CS heterostructure, has been successfully produced with sharp interfaces by molecular-beam epitaxy on 2-inch wafers. By performing elemental specific X-ray magnetic circular dichroism (XMCD) measurements, we have unequivocally discovered that TC of 4-layer Fe3GeTe2 can be significantly enhanced from 140 K to 230 K because of the interfacial ferromagnetic coupling. Meanwhile, an inverse proximity effect occurs in the FGT/CS interface, driving the interfacial antiferromagnetic CrSb into a ferrimagnetic state as evidenced by double-switching behavior in hysteresis loops and the XMCD spectra. Density functional theory calculations show that the Fe-Te/Cr-Sb interface is strongly FM coupled and doping of the spin-polarized electrons by the interfacial Cr layer gives rise to the TC enhancement of the Fe3GeTe2 films, in accordance with our XMCD measurements. Strikingly, by introducing rich Fe in a 4-layer FGT/CS superlattice, TC can be further enhanced to near room temperature. Our results provide a feasible approach for enhancing the magnetic order of few-layer 2D FMs in wafer-scale and render opportunities for realizing realistic ultra-thin spintronic devices.  相似文献   

19.
Lithium titanium oxide (Li4Ti5O12, LTO), a ‘zero-strain’ anode material for lithium-ion batteries, exhibits excellent cycling performance. However, its poor conductivity highly limits its applications. Here, the structural stability and conductivity of LTO were studied using in situ high-pressure measurements and first-principles calculations. LTO underwent a pressure-induced amorphization (PIA) at 26.9 GPa. The impedance spectroscopy revealed that the conductivity of LTO improved significantly after amorphization and that the conductivity of decompressed amorphous LTO increased by an order of magnitude compared with its starting phase. Furthermore, our calculations demonstrated that the different compressibility of the LiO6 and TiO6 octahedra in the structure was crucial for the PIA. The amorphous phase promotes Li+ diffusion and enhances its ionic conductivity by providing defects for ion migration. Our results not only provide an insight into the pressure depended structural properties of a spinel-like material, but also facilitate exploration of the interplay between PIA and conductivity.  相似文献   

20.
Prostaglandins and (PG) have been reported to be an important gastric acid suppressive factor. However, the mechanism underlying is yet to be clearly established. In vitro study with gastric microsomes in presence of both PGE2 and PGI2 shows a stimulation of gastric H+ K+-ATPase activity below 1X10−6M and 2.5X10−7M concentrations respectively. However, with further increase in concentrations of both PGE2 and PGI2, H+, K+-ATPase activity shows an inhibition but PGI2 completely obliterates the K+ stimulated part of H+, K+-ATPase activity at higher concentration. The H+-ion transport study using chambered frog gastric mucosa shows that both PGE2 and PGI2 inhibit H+-ion transport at 5X10−6 M and 10X10−6M concentrations respectively but the effect of PGI2 is reversible. These differential effects of PGE2 and PGI2 on microsomal H+, K+-ATPase and on H+ transport my be caused by the differential effects of these phospholipid mediators with the gastric mucosal cell membrane. This in vitro investigation shows the role of prostaglandin (s) as a physiological switch/regulator of gastric H+ ion transport leading to the cessation of gastric acid secretion.  相似文献   

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