Ex-situ Scanning Electron Microscopy Research Articles

Multi-diagnostic of dust growth in a capacitive Ar/C2H2 plasma

Abstract The interest in the production of nanoparticles (NPs) within Ar/C2H2 reactive plasmas is increasing, driven by their potential applications in functional materials or for their analogy to cosmic dust. The growth process of NPs has been thoroughly examined using a broad array of diagnostic tools. Significant among these tools are those that determine two-dimensional distributions of NP sizes and densities. The inherent complexity of these techniques has resulted in a limited number of works that integrate these measurements with a multitude of other diagnostic tools. Here, we show a multi-diagnostic exploration of the growing process of NPs in Ar/C2H2 plasmas. The combination of in-situ techniques, such as scattered light images, optical emission spectroscopy, light extinction, quadrupole mass signals, or self-bias voltage, with ex-situ scanning electron microscopy images and FTIR spectra of the deposited dust, provides a detailed picture of the growth process. The temporal evolution of plasma parameters, coupled with chemical composition measurements, provides a comprehensive description of the dust growth phases, and the FTIR measurements reveal an appreciable difference in chemical composition between the core and shell of the NPs. Furthermore, employing a method based on the terminal falling velocity of NPs in the afterglow, the intrinsic mass density of NPs is estimated. The asymmetries observed in the spatial distributions of NP size and density are qualitatively discussed in terms of neutral drag, ion drag, and electrostatic forces.

Complex precipitation behavior in a Co-free high entropy alloy during aging

High entropy alloys (HEAs) demonstrate high strength, thermal stability, and irradiation resistance, making them desirable for applications in nuclear reactors and other harsh environments. Many existing HEAs contain cobalt (Co), which makes them unsuitable for nuclear applications due to the long-term activation of Co. A previously studied Co-free alloy, (Fe0.3Ni0.3Mn0.3Cr0.1)88Ti4Al8, exhibits high strength but compromised ductility due to its network of brittle precipitates upon aging. This work investigates the formation mechanism and evolution of the precipitates, including L12 (Ni3Ti type, ordered face-centered cubic structure), B2 (NiAl type, ordered body-centered cubic structure), and Chi (FeCr-rich ordered α-Mn structure), in this alloy at 650 °C, the aging temperature that yields the alloy’s peak strength after 120 hours. Using ex-situ scanning electron microscopy, transmission electron microscopy, and atom probe tomography, the precipitates were characterized in terms of their composition, morphology, and crystal structure at various aging times. In addition, synchrotron-based, in-situ X-ray diffraction was used to probe the evolution of precipitates in the bulk during key phases of in-situ aging. The L12 precipitates exhibit complex growth and coarsening behavior – their coarsening starts after just 24 hours, and competition between the L12 and B2 phases arises after 72 hours leading to a decrease in L12 volume fraction. Conversely, B2 and Chi precipitates exhibit delayed nucleation and growth, and do not form in observable quantities until after 24 hours. Once formed, however, these precipitates quickly dominate the microstructure, with >50 % volume fraction after 120 hours, leading to the previously observed mechanical properties. This study provides a foundational understanding of the evolution of multi-precipitate structures in HEAs and guides future alloy development and optimization by tailoring the precipitates.

The effect of reserved shish content on the structural evolution of high-entanglement ultrahigh molecular weight polyethylene films during the hot stretching process

To explore novel approaches facilitating the structural evolution of high-entanglement ultrahigh molecular weight polyethylene (UHMWPE) films, this study precisely controlled the temperature during compression molding to successfully prepare high-entanglement UHMWPE films with different shish contents. Using in-situ small-angle X-ray scattering (SAXS)/ultra-small-angle X-ray scattering (USAXS)/wide-angle X-ray diffraction (WAXD) alongside ex-situ scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), we investigated the influence of shish contents on the structural evolution of high-entanglement UHMWPE films during hot stretching. The results indicate that increasing shish content in high-entanglement UHMWPE films reduces the accumulation of inclined lamellar crystals caused by high entanglement, promoting the transformation of inclined lamellar crystals into shish-kebab crystals and facilitating the formation of more shish-kebab crystals. In high-entanglement UHMWPE films with high shish content, eventually, all inclined lamellar crystals even transform into shish-kebab crystals.

Li-Ion Intercalating Cathode for Advanced Lithium-Sulfur Batteries

The advancement of lithium-sulfur (Li-S) batteries represents a significant shift in high-energy-density electrochemical storage, offering energy densities far exceeding those of traditional lithium-ion systems. This research contributes to the evolving field of Li-S batteries by proposing a novel strategy to optimize cathode performance, crucial in harnessing their full potential.Li-S batteries are characterized by their unique electrochemical process, which involves converting elemental sulfur to lithium sulfide (Li2S) during discharge via lithium polysulfide intermediates. A traditional challenge in this process is the notorious shuttle effect caused by lithium polysulfide intermediates. These intermediates, highly soluble in standard electrolytes, migrate continuously between the cathode and anode, leading to substantial active material loss, rapid capacity degradation, and reduced coulombic efficiency. Significant advancements have been made by introducing metal compounds with a chemical affinity for lithium polysulfides. However, a persistent challenge remains: the insulating nature of Li2S, which hinders electron transport. Recent strategies aiming to address these issues have focused on electrolytes with enhanced Li2S solubility to promote three-dimensional (3D) Li2S growth and prevent cathode passivation. Yet, the increased reactivity of such electrolytes poses new challenges, highlighting the need for alternative solutions.Our study explores this challenge, utilizing lithiated metal oxides as intercalating cathode materials to control Li2S growth dynamics. This method offers immediate mitigation of side reactions in the implementation of enhanced electrolytes. The scope of our research encompasses the thorough synthesis and characterization of these intercalating oxides, emphasizing their role in control Li2S growth. Additionally, we delve into the electrochemical characterization of these materials, focusing on their lithiation/delithiation kinetics and the consequent impact on Li-S battery performance. These intercalating oxides, capable of incorporating lithium ions within their crystal structure, present a promising path for aligning lithiation with Li2S formation, thereby fostering effective 3D growth. This contrasts with other oxides where asynchronous lithiation results in conventional two-dimensional (2D) Li2S growth, leading to premature discharge termination and suboptimal battery performance.We introduce a mechanism where 3D Li2S growth is driven by enhanced solvation of Li2S, intricately linked to the lithiation behavior of these oxides. By incorporating these optimized intercalating oxides in Li-S cells, we observe notable improvements in discharge capacity and sulfur utilization. This improvement is especially significant under high sulfur loading conditions, which typically exacerbate the polysulfide shuttle effect and pose formidable challenges for Li-S battery efficiency. Our investigation includes a detailed morphological analysis of Li2S deposition on various cathode surfaces. Employing advanced techniques like ex-situ Scanning Electron Microscopy (SEM) and electrodeposition modeling, we discern distinct Li2S growth patterns. These findings reveal that cathodes incorporating specific intercalating oxides exhibit reduced surface passivation due to predominant 3D Li2S growth, as opposed to the 2D growth observed in other oxide substrates. This variation in growth morphology significantly impacts cell performance, particularly under high sulfur loading conditions, where effective management of Li2S formation and polysulfide shuttling is crucial.In conclusion, this research marks a significant step in addressing the fundamental challenges of Li-S batteries. By leveraging the distinct properties of select intercalating oxides, the study not only deepens our understanding of Li2S growth mechanisms but also demonstrates an effective method to enhance Li-S battery performance. This work lays a foundation for future developments in high-energy-density battery technologies and signifies a crucial advancement towards the realization of more efficient and robust Li-S batteries.

Unveiling the Mechanical and Electrochemical Evolution of Nanosilicon Composite Anodes in Sulfide-Based All-Solid-State Batteries

The utilization of silicon (Si) anodes in all-solid-state lithium batteries (ASLBs) provides the potential for high energy density. However, the compatibility of sulfide solid-state electrolytes (SEs) with Si and carbon is often questioned due to potential decomposition. To investigate this, operando X-ray absorption near-edge structure (XANES) spectroscopy, ex-situ scanning electron microscopy (SEM) and ex-situ X-ray nano-tomography (XnT) were utilized to study the chemistry and structure evolution of nano Si composite anodes. Results from XANES demonstrated a partial decomposition of SEs during the first lithiation stage, which was further accelerated by the presence of carbon. But the performance of first three cycles in Si-SE-C was stable, which proved the generated media is ionically conductive. XnT and SEM results showed that the addition of SEs and carbon improved the structural stability of the anode with fewer pores and voids. A chemo-elasto-plastic model revealed that SEs and carbon buffered the volume expansion of Si, thus enhancing mechanical stability. The balance between the pros and cons of SEs and carbon in enhancing reaction kinetics and structural stability enabled the Si composite anode to demonstrate the highest Si utilization with higher specific capacities and better rate than pure Si and Si composite anodes with only SEs.

Structural Regulation of NiFe LDH under Spontaneous Corrosion to Enhance the Oxygen Evolution Properties.

Electrochemical water splitting holds promise for sustainable hydrogen production but restricted by the sluggish reaction kinetics at the anodic oxygen evolution. Herein, we present a room-temperature spontaneous corrosion strategy to convert inexpensive iron (Fe) on iron foam substrates into highly active and stable self-supporting nickel iron layered hydroxide (NiFe LDH) catalysts. The corrosion evolution mechanisms are elucidated combining ex-situ scanning electron microscopy (SEM) and X-ray photo electron spectroscopy (XPS) techniques, demonstrating precise control over the concentration of Ni2+ and reaction time to achieve controllable micro-structures of NiFe LDH. Taking advantage of the self-supporting morphology and hierarchical micro-/nano- structure, the NiFe LDH with optimized Ni2+ concentration and reaction time exhibits significant small overpotentials of 160 mV and 200 mV for the OER at current densities of 10 mA cm-2 and 100 mA cm-2 respectively, showcasing excellent OER activities. Furthermore, this catalyst demonstrates superior reaction kinetics, high electrochemical stability, and excellent integral water splitting performance when coupled with a commercial Pt/C cathode. The energy-efficient, cost-effective, and scalable spontaneous corrosion strategy opens new avenues for the development of high-electrochemical-interface catalysts.

Tailored crystal planes of VO2 cathode power fast Zn2+ storage

Vanadium dioxide (VO2) cathode with specific tunnel structure and favorable specific capacity is critical for developing aqueous zinc-ion batteries (AZIBs) with excellent electrochemical performance. However, sluggish electrochemical kinetics hampered its development in burgeoning energy storage devices. Herein, we tailored VO2 material with different exposed crystal planes and employed as cathodes for AZIBs. The comprehensive analyses indicate the exposed (201) and (001) crystal planes are favorable for fast electrochemical kinetics, high capacitance storage, and the smallest diffusion energy barrier, which guarantee electrodes with high discharge capacity (367 mA h/g at 0.1 A/g), excellent rate capability (281 mA h/g at 4 A/g) and cycling stability over 800 cycles. Besides, Ex-situ characterizations manifest VO2 cathode with specific exposed crystal planes easily transformed to Zn3+x(OH)2V2O7·2H2O in the first discharge process, hence allowing continuous embedding of Zn2+ in this layered structure, and the ex-situ scanning electron microscopy (SEM) analysis confirms the morphology change matched well with the structural transformation. This study may enlighten and promote the role of exposed crystal plane to develop high-performance rechargeable batteries.

Plasmonic properties and stability of Au and Cu nanoparticles embedded in cerium oxide

With the aim of sensitizing cerium oxide—a very important catalytic material—to visible light, its coupling with Au and Cu nanoparticles is investigated. The samples are grown by physical synthesis by embedding a layer of nanoparticles between two cerium oxide films. The films are controlled in composition by in-situ x-ray photoemission spectroscopy and in morphology by ex-situ scanning electron microscopy. The optical properties as a function of the oxide thickness, investigated by spectrophotometry in the UV-Vis range, are interpreted based on the results of the morphological characterization and of simulations based on the Maxwell Garnett model. The stability of chemical and optical properties after air exposure is also investigated. The results, indicating that stable materials with tuneable optical properties can be obtained, are important in view of the potential application of the investigated systems in photocatalysis.

Bi Nanospheres Embedded in N-Doped Carbon Nanowires Facilitate Ultrafast and Ultrastable Sodium Storage.

Sodium ion batteries (SIBs) are considered as the ideal candidates for the next generation of electrochemical energy storage devices. The major challenges of anode lie in poor cycling stability and the sluggish kinetics attributed to the inherent large Na+ size. In this work, Bi nanosphere encapsulated in N-doped carbon nanowires (Bi@N-C) is assembled by facile electrospinning and carbonization. N-doped carbon mitigates the structure stress/strain during alloying/dealloying, optimizes the ionic/electronic diffusion, and provides fast electron transfer and structural stability. Due to the excellent structure, Bi@N-C shows excellent Na storage performance in SIBs in terms of good cycling stability and rate capacity in half cells and full cells. The fundamental mechanism of the outstanding electrochemical performance of Bi@N-C has been demonstrated through synchrotron in-situ XRD, atomic force microscopy, ex-situ scanning electron microscopy (SEM) and density functional theory (DFT) calculation. Importantly, a deeper understanding of the underlying reasons of the performance improvement is elucidated, which is vital for providing the theoretical basis for application of SIBs.

Top-down nanostructured multilayer MoS2 with atomically sharp edges for electrochemical hydrogen evolution reaction

Cost-efficient and readily scalable platinum-free electrocatalysts are crucial for a smooth transition to future renewable energy systems. Top-down activation of MoS2 promises the production of sustainable hydrogen evolution electrocatalysts from the Earth-abundant molybdenite ore. Here, the deterministic nanopatterning of multilayer MoS2 with numerous zigzag edges is explored as a pathway to enhance hydrogen evolution reaction (HER). Nanopatterned single-nanosheet MoS2 electrodes are assessed by two highly localized electrochemical techniques: selected area voltammetry (with lithography-defined regions of electrode-electrolyte contact) and Scanning ElectroChemical Microscopy (SECM). The nanopatterning effect is the most pronounced after prolonged electrochemical cycling in an acidic electrolyte. The electrocatalytic hydrogen evolution activity of edge-enriched electrodes is dramatically enhanced: the maximum electrochemical current density (jmax) achieved at -510 mV vs. reversible hydrogen electrode (mVRHE) is increased by two orders of magnitude, reaching >300 mA⋅cm−2. Both the η10 and η100 overpotentials are significantly reduced as well. Meanwhile, pristine MoS2 shows just ≈6 times jmax increase (≈30 mA⋅cm−2) after the very same cycling. The increased electrocatalytic activity comes with electrode morphology degradation, evidenced by ex-situ scanning electron microscopy. SECM directly visualizes stronger HER activity in the regions with densely located zigzag edges. Intense white light illumination significantly boosts HER on MoS2 electrodes due to the photo-enhanced MoS2 conductivity. These results improve the understanding and reveal the limitations of MoS2-based electrocatalytic water splitting.

Ex-situ observation of the short crack initiation and propagation behaviour of nickel-base wrought alloy Inconel 718 for critical rotating components under fatigue conditions at elevated temperatures

In this paper, the initiation and propagation behaviour of short fatigue cracks in nickel-base alloy Inconel 718 is studied extensively in the fatigue loading regime by ex-situ scanning electron microscopy on component-near notched specimens in the temperature range between 400°C and 600°C. To investigate the influence of different surface treatments, both specimens with polished and shot-peened surfaces were tested. For polished specimens, most fatigue cracks initiated at oxidised non-metallic inclusions, whereas for shot-peened specimens, the process-induced surface roughness also served as crack starters. It was found, that the observed scatter in lifetime for repetitive tests is mainly caused within the short crack fatigue regime below 50μm, while cracks larger than 100μm showed similar growth characteristics.

In-situ constructing porous N-doped carbon skeleton with rich defects from modified polyamide acid to boost the high performance of Na3V2(PO4)3 cathode for full sodium-ion batteries

Generally, the transport of electrons and Na+ is seriously constrained in Na3V2(PO4)3 (NVP) due to intense interactions of V-O and PO bonds. Besides, polyamide acid (PAA) is hardly used in the sol–gel route due to insolubility. This work develops a facile liquid synthesis strategy based on modified PAA, achieving in-situ construction of a porous N-doped carbon framework with rich defects to improve the kinetics of NVP. The addition of triethylamine (TEA) reacts with carboxyls in PAA to achieve acid-base neutralization, turning PAA into polyamide salts with good solubility. The special morphology construction mechanism of this unique system was observed by ex-situ scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). Specifically, PAA undergoes in-situ conversion into chain-like polyimide (PI) through a thermal polymerization mechanism during the pre-sintering process. Meanwhile, NVP precursors are evenly dispersed in the PI fibers, efficiently reducing the particle size. After the final treatment, the favorable porous carbon skeleton could be generated derived from the partial decomposition of PI, on which small active grains are in situ grown. The resulting N-doped carbon substrate contains rich defects, benefiting from the migration of Na+. Furthermore, the porous construction is conducive to alleviating the stress and strain generated by the high current impact, increasing the contact area between electrodes/electrolytes to improve the utilization efficiency of active substances. Comprehensively, the optimized samples exhibit a capacity of 82.1 mAh g−1 at 15C with a retention rate of 95.45 % after 350 cycles. It submits a capacity of 67.6 mAh g−1 at 90C and remains 52.2 mAh g−1 after 1500 cycles. Even in full cells, it reveals a value of 110.6 mAh g−1. This work guides the application of in-situ multiple modifications of polymers in electrode materials.

Porous lithiophilic Cu-Sn solid solution current collector for dendrite-free lithium metal batteries

Lithium metal batteries (LMBs) have high energy density but suffer from the formation of Li dendrites and unstable solid electrolyte interface. Herein, a three-dimensional porous Cu-Sn solid solution was designed as current collector for LMBs and was fabricated through the combination of vapor phase alloying with subsequent vapor phase dealloying. The effect of the Sn addition on electrochemical performances and Li plating/stripping behaviors was investigated using in-situ X-ray diffraction, ex-situ scanning electron microscopy, as well as density functional theory calculations. As benchmarked with porous Cu (3D-Cu), the addition of lithiophilic Sn can efficiently improve the Li plating/stripping performance, especially for the 1.5 at.% Sn addition (3D-Cu98.5Sn1.5). The 3D-Cu98.5Sn1.5 current collector maintains coulombic efficiency of 95 % up to 200 cycles at 1 mA cm−2. Moreover, the existence of Sn in solid solution exhibits a much lower binding energy (-3.223 eV) and nucleation overpotential (28.9 mV) compared with those of 3D-Cu, indicating that the metallic Li is extremely susceptible to nucleation and growth on the surface. Additionally, the gas evolution scenarios were probed by on-line differential electrochemical mass spectrometry. Our findings show that the 3D-Cu98.5Sn1.5 current collector effectively enhances the uniformity of Li plating and suppresses the generation of dendrites in LMBs.

Co-Fe Prussian blue analogue ultrafine nanocrystal cubes grown in-situ in honeycomb carbon as high-performance anode for lithium-ion batteries

Prussian blue analogues (PBAs) are promising anode materials for lithium-ion batteries due to the unique 3D open frameworks, but inferior cycling performance and poor rate capability restrict their application. Herein, Co-Fe PBA@honeycomb carbon is prepared by means of well-designed solution evaporation assembly and in-situ etching-coordination strategy. K0.90Co[Fe(CN)6]0.97□0.03⋅0·.44H2O (□: vacancy defect) cubes with uniform size of 20 nm are grown within every honeycomb carbon pore with a diameter of ∼ 180 nm. The mass content of Co-Fe PBA reaches 78.61 wt%. The small size, low defects and less interstitial/coordinated water improve kinetics properties and robustness of Co-Fe PBA. Honeycomb carbon further enhances the electronic conductivity and structural stability of Co-Fe PBA. Accordingly, Co-Fe PBA@honeycomb carbon exhibits high reversible capacities of 915 mAh/g at 0.5 A/g after 200 cycles, 658 mAh/g at 1 A/g after 1000 cycles, 496 mAh/g at 2 A/g after 450 cycles. Rate performance and kinetics properties are superior. The reversible capacity at 5 A/g is as high as 328 mAh/g. The diffusion coefficient of Li+ reaches 10−10.0 ∼ 10−11.7 cm2 s−1. Ex-situ scanning electron microscopy and Fourier transform infrared spectrometer demonstrate that the cycled Co-Fe PBA@honeycomb carbon is stable.

Phase-separated bimetal enhanced sodium storage: Dimer-like Sn-Bi@C heterostructures with high capacity and long cycle life

Phase boundaries facilitate the charge transportation and alleviate the intrinsic stress upon cycles. Therefore, how to achieve regular phase boundaries is very attractive. Herein, dimer-like Sn-Bi@C nanostructures, where is a well-defined phase boundary between Sn and Bi, have been prepared by a two-step process for the first time. The phase boundary not only provides additional and fast transportation for Na+, but also mitigates the structure stress/strain upon cycling. Therefore, Sn-Bi@C exhibits a high capacity (472.1 mA h g−1 at 2 A g−1 for 200 cycles), an ultra-long cyclic life (355.6 mA h g−1 at 5 A g−1 for 4500 cycles) and an excellent rate performance (372 mA h g−1 at 10 A g−1) for sodium storage, much higher than those of Sn@C, Bi@C, and Sn@C + Bi@C. Notably, the full cells of Sn-Bi@C//Na3V2(PO4)3/rGO (Sn-Bi@C//NVP/rGO) demonstrate impressive performance (323 mA h g−1 at 2 A g−1 for 300 cycles). The underlying mechanism for such an excellent performance is elucidated by in-situ X-ray diffraction, ex-situ scanning electron microscopy /high-resolution transmission electron microscopy and atomic force microscopy, revealing the good electrode stability and improved mechanical properties of Sn-Bi@C. The synthetic method is extended to dimer-like Sn-Pb@C and Sn-Ag@C heterostructures, which also exhibit the good cycle stability for sodium storage.

Three-dimensional Ag/carbon nanotube-graphene foam for high performance dendrite free lithium/sodium metal anodes

• Porous 3D Ag/CNT-GF structure effectively alleviates the volume expansion of Li/Na. • Lithiophilic/sodiophilic Ag NPs directionally guide Li/Na deposition. • Dendrite free morphology is achieved in Li/Na@3D Ag/CNT-GF anodes. Although lithium metal and sodium metal are promised as ideal anodes for lithium ion batteries (LIBs) and sodium ion batteries (SIBs), they still suffer from inevitable dendrite growth. In light of this, silver nanoparticles (Ag NPs) are sputtered onto three-dimensional carbon nanotube decorated graphene foam (3D CNT-GF) to construct superior 3D Ag/CNT-GF composite matrix for lithium metal anodes (LMAs) and sodium metal anodes (SMAs). With this design, lithiophilic/sodiophilic Ag NPs could provide favorable sites to guide Li/Na metal nucleation and growth, thus leading to low nucleation overpotentials, high Coulombic efficiency and long cycle performance. Accordingly, 3D Ag/CNT-GF electrodes can stably cycle for 1000 and 750 cycles at 3 mA cm −2 with 1 mAh cm −2 for SMAs and LMAs, respectively. More attractively, it can also stably sustain 300 cycles (SMAs) and 500 cycles (LMAs) at a large current density of 5 mA cm −2 with 1 mAh cm −2 . The excellent electrochemical performance can be attributed to the lithiophilic/sodiophilic electrode surface, 3D porous electrode structure and the dendrite-free morphology as demonstrated by ex-situ scanning electron microscopy (SEM) and in-situ optical microscopy analyses. Furthermore, full cells based on Na@3D Ag/CNT-GF||Na 3 V 2 (PO 4 ) 3 @carbon (NVP@C) and Li@3D Ag/CNT-GF||LiFePO 4 (LFP) could deliver highly reversible capacities of 90.1 and 106.4 mAh g −1 respectively at 100 mA g −1 after 200 cycles for SIBs and LIBs, respectively. This work demonstrates a novel 3D Ag/CNT-GF matrix for boosting Li/Na deposition stability for their future applications. Porous 3D Ag/CNT-GF nanostructure was designed and further adopted as the stable host of lithium/sodium metal anodes. Lithiophilic/sodiophilic Ag NPs directionally guide Li/Na deposition with uniform current density distribution over the 3D Ag/CNT-GF current collector surface, enabling a dendrite free deposition morphology and long cycle stability.

Dealloying-induced modulation upon porous layer depth of three-dimensional copper current collector for improving lithium plating/stripping capability

Lithium metal anode has shown great potentials for achieving high energy density due to its high theoretical capacity and low redox potential, but its application is impeded by the dendrite proliferation and unstable solid electrolyte interface. Herein, three-dimensional (3D) porous Cu current collectors were fabricated via the combination of painting-alloying-dealloying with subsequent annealing, where the depth and length scale of the porous layer can be facilely regulated by controlling the alloying and annealing processes. In lithium metal batteries, the relationship between the Li deposition behavior and the porous layer depth was explored in detail via electrochemical measurements and ex-situ scanning electron microscopy. Notably, the A-3D Cu-14 current collector with the porous layer depth of around 34.5 µm exhibits long lifespan over 430 h at 1 mA cm−2 and low voltage hysteresis, in comparison with the pristine Cu foil and the porous Cu with thinner porous layers. The superior electrochemical performance of A-3D Cu-14 can be attributed to the enhanced suppression effect upon the Li dendrite deriving from the more accommodation capability of its thick porous layer, as well as the better homogenization of the Li+ ion flux caused by the porous structure. Furthermore, the Li@A-3D Cu-14 | LiFePO4 full cell shows excellent cycling stability and rate capability in full battery tests.

(Digital Presentation) Influence of Li2s on the Volume Expansion of Sn Particles during Lithiation of Tin Sulfides

In recent years tin sulfides, particularly SnS and SnS2, have attracted significant attention in the energy storage research community. Their high theoretical specific capacities (1111 mAhg-1 for SnS and 1209 mAhg-1 for SnS2) make this group of materials good candidates for anode active materials for Li-ion batteries. Moreover, their low cost and environmental benignity further contribute to the appeal. During lithiation, tin sulfides undergo a conversion reaction with Li in which Li2S and Sn are formed. Further lithiation triggers the alloying reaction between Sn and Li, resulting in the formation of various Sn-Li intermetallic phases. The newly formed Sn-Li phases have a significantly higher unit cell volume than their parent phases, causing cracking of particles on repeated alloying and dealloying. Ultimately, the continuous cracking of particles leads to pulverization of anode material, reduced contact between the particles and capacity fade.In our work, we explored the influence of Li2S formed during the conversion reaction on the stability of the solid electrolyte interphase (SEI) layer and the overall cycling performance of SnS and SnS2 materials. The precipitation reaction was used to synthesised both SnS and SnS2 materials. Furthermore, SnS2 was also synthesised via the widely used hydrothermal method. In all cases, SnClx ·yH2O (x= 2; y= 2 for SnS and x= 4; y= 5 for SnS2) was used as a Sn source and thioacetamide as a S source. The physio-chemical properties of the as-synthesised materials were examined by powder X-ray diffraction (PXRD) and structural parameters were extracted using Rietveld analysis of the measured patterns. Furthermore, the sample morphologies were characterized by scanning electron microscopy (SEM) and the crystallinity of the samples was further investigated by transmission electron microscopy (TEM). The presence of surface impurities which may formed during material synthesis, was examined by X-ray photoemission spectroscopy (XPS).The cycling performance of SnS2 prepared via the precipitation reaction was compared to SnS2 prepared via hydrothermal method as well as to SnS prepared via precipitation reaction. In this way we were able to draw comparisons between materials with the same chemical composition but different particle size and morphology as well as materials with different chemical composition and very similar morphology.The length changes of SnS and SnS2 electrodes during cycling were investigated by the in-situ dilatometry technique, and several ex-situ methods such as ex-situ XRD and ex-situ SEM were utilized to investigate the role of crystal chemistry and particle morphology on electrochemical performance post-mortem. The results showed that on alloying, the electrode comprised of partially amorphous SnS2 synthesised via the precipitation expands the least. Additionally, the cycling data show that partially amorphous SnS2 electrochemically outperformed both SnS and highly crystalline SnS2. This may be attributed to two effects. Firstly, thicker Li2S layers are generally formed on particles with lower surface areas, thereby better restraining the volume changes of Sn during cycling. Secondly, due to the intercalation step prior to the conversion reaction in SnS2, it is postulated that Li2S and Sn are homogeneously distributed on the atomic scale, which further helps to minimize the volume expansion during cycling.

Effect of HF etching on titanium carbide (Ti3C2Tx) microstructure and its capacitive properties

Two-dimensional multi-layered microstructure generated by hydrofluoric acid etching is essential for the high capacitance MXenes. However, the mechanisms dictating the formation, evolution and properties of MXenes during etching remain elusive due to the lack of direct observation. Herein, using ex-situ scanning electron microscopy combined with high resolution transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy, we have revealed the fine variation of microstructure and properties of multi-layered titanium carbide Ti3C2Tx etched for different time. The results show that the laminar cracks always formed from the first initial laminar crack at the edge site of the outermost side of the Ti3AlC2 particle, which induces continuous nucleation of other laminar cracks in the nearby area. The early laminar cracks undergo growth accompanying with increased macro-layer density of Ti3C2Tx and the Al(F,O,C)3 precipitation in subsequent etching process. The formation of laminar cracks is revealed to be correlated with the release of local internal stress in Ti3AlC2. In addition, it is found that there are significant changes of Ti valence state, CC and Ti-C bonding as well as Ti-F, CO and Al-O surface groups during etching. Maximum specific capacitance coincides with maximum lattice parameter c of Ti3C2Tx and maximum number of macro-layers, while over-etching produces in-plane microcracks, Ti dissolution, and reduced specific capacitance. The results provide important insight to facilitate optimal synthesis of this material.

Homogeneous electric field and Li+ flux regulation in three-dimensional nanofibrous composite framework for ultra-long-life lithium metal anode

Lithium (Li) metal is considered as the best anode candidate for next-generation high-energy batteries due to its ultralow electrochemical potential and extremely high theoretical capacity. However, issues arising from the undesired growth of lithium dendrites and infinite volumetric change have seriously hindered the practical application of lithium metal batteries (LMBs). Here, we designed a super-lithiophilic amorphous zinc oxide-doped carbon nanofiber framework with uniformly-distributed and parallel multichannels (MCCNF@ZnO) to achieve the homogeneous distribution of electric field and Li+ flux. By the assistances of COMSOL Multiphysics simulations and ex-situ scanning electron microscopy, we reveal that the Li metal preferentially deposits into the porous nanochannels inside the nanofibers, followed by its even distribution on the lithiophilic surface of MCCNF@ZnO. Furthermore, the conductive multichannels of the carbon nanofiber skeleton can effectively minimize the partial current density, thereby effectively avoiding the electrochemical polarization and assisting the uniform metallic deposition. As a result, MCCNF@ZnO exhibits a stable CE over 99.2% as the substrate after 500 cycles at the current density of 1 mA cm−2. The symmetrical cell of lithium-loaded MCCNF@ZnO composite electrodes can stably operate over 3300 h at 0.5 mA cm−2, indicating the great potential of MCCNF@ZnO for stabilizing lithium metal anodes in practical applications of LMBs.