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Binary metal sulfides have been explored as sodium storage materials owing to their high theoretical capacity and high stable cyclability. Nevertheless, their relative high charge voltage and relatively low practical capacity make them less attractive as an anode material. To resolve the problem, addition of alloying elements is considerable. Copper antimony sulfide is investigated as a representative case. In this study, we do not only perform electrochemical characterization on CuSbS2, but also investigate its nonequilibrium sodiation pathway employing in-/ex situ transmission electron microscopy, in situ X-ray diffraction, and density functional theory calculations. Our finding provides valuable insights on sodium storage into ternary metal sulfide including an alloying element.

Graphene liquid cell electron microscopy (GLC-EM), a cutting-edge liquid-phase EM technique, has become a powerful tool to directly visualize wet biological samples and the microstructural dynamics of nanomaterials in liquids. GLC uses graphene sheets with a one carbon atom thickness as a viewing window and a liquid container. As a result, GLC facilitates atomic-scale observation while sustaining intact liquids inside an ultra-high-vacuum transmission electron microscopy chamber. Using GLC-EM, diverse scientific results have been recently reported in the material, colloidal, environmental, and life science fields. Here, the developments of GLC fabrications, such as first-generation veil-type cells, second-generation well-type cells, and third-generation liquid-flowing cells, are summarized. Moreover, recent GLC-EM studies on colloidal nanoparticles, battery electrodes, mineralization, and wet biological samples are also highlighted. Finally, the considerations and future opportunities associated with GLC-EM are discussed to offer broad understanding and insight on atomic-resolution imaging in liquid-state dynamics.

The development of high-tap density electrode materials that can simultaneously achieve stable electrochemical performance at high charge/discharge rates is critically in demand. Herein, we propose an innovative material design that can offer high tap density and excellent rate capabilities by using Co3O4 nanograin-interconnected secondary particles (Co3O4 NISPs). By taking advantage of a conversion reaction that forms Co from Co3O4, we demonstrate that Co3O4 NISPs are capable of creating a number of metallic Co sites along with a number of vacant sites in-between nanograins. Electrochemical tests that reveal reduced internal cell resistance and more accessible Li diffusion are achieved for Co3O4 NISPs compared with Co3O4 nanoparticles (NPs). Additionally, in situ X-ray diffraction (XRD) analyses, electron energy loss spectroscopy (EELS), and density functional theory (DFT) calculations reveal that the insulating intermediate product (CoO) is formed less on the Co3O4 NISPs, which can enhance the charge transport. Attributed to the combinatorial effects of Co3O4 nanograins that form metallic Co upon conversion and secondary particles that enable high tap density, Co3O4 NISPs show the most outstanding volumetric capacity (2167.3 mA h cm−3 at a current density of 500 mA g−1) among spinel-type metal oxide electrode materials researched so far.

The development of high performance and cost-effective electrode materials is the main challenge for the commercialization of sodium ion batteries. Here, we suggest a substantial iron-doped sodium vanadium fluorophosphate and sodium vanadium phosphate composite as a promising cathode. Iron substitution enhances ionic diffusivity and lowers the bandgap, and, thus, improves sodium storage performance. The origin of the enhanced performance is investigated employing in situ X-ray diffraction, ex situ X-ray photoelectron spectroscopy, density functional theory calculation, and electrochemical characterization. Moreover, we demonstrate its full cell configuration with earth-abundant element-based copper sulfide anodes. The suggested cathode and sodium ion battery full cell exhibits well-balanced sodium storage performance in terms of energy density, C-rate capability, cycling stability, and low cost. The low cost and high performance of the full cell make it an attractive choice for energy storage systems and high power applications to support lithium ion batteries.

Binary metal sulfides have been explored as sodium storage materials owing to their high theoretical capacity and high stable cyclability. Nevertheless, their relative high charge voltage and relatively low practical capacity make them less attractive as an anode material. To resolve the problem, addition of alloying elements is considerable. Copper antimony sulfide is investigated as a representative case. In this study, we do not only perform electrochemical characterization on CuSbS

As it governs the overall performance of lithium-ion batteries, understanding the reaction pathway of lithiation is highly desired. For Co3O4 nanoparticles as anode material, here, we report an initial conversion reaction pathway during lithiation. Using graphene liquid cell electron microscopy (GLC-EM), we reveal a CoO phase of the initial conversion product as well as morphological dynamics during Co3O4 lithiation. In accordance with the in situ TEM observation, we confirmed that the Co3O4 to CoO conversion is a thermodynamically favorable process by calculating the theoretical average voltage based on density functional theory. Our observation will provide a useful insight into the oxide electrode that undergoes conversion reaction.

Development of feasible electrode materials is significant to realize high energy density Li-ion batteries (LIBs). Tin(IV) oxide, in particular, has a number of merits including higher theoretical capacity compared with graphite (1493 mAh g–1), low cost, and environmental friendliness. Nevertheless, huge volume changes and subsequent pulverization usually resulted in poor capacity retention of SnO2, where various nanostructures have been adopted to overcome its intrinsic limitations. Here we introduce the new insights into employing polycrystalline dense SnO2 nanospheres (NSs), rather than its hollow structures, as high-performance electrode for LIBs. Contrary to the previous notions, polycrystalline dense SnO2 NSs can exhibit highly stable cycle retention characteristics (1009.9 mAh g–1 after 300 cycles at 0.5 A g–1) as well as considerable rate capabilities (349 mAh g–1 at 5.0 A g–1), even superior to those of polycrystalline hollow SnO2 NSs. Based on the in situ TEM analyses and electrochemical/postmor...

The mineralization dynamics of calcium carbonate is investigated under highly supersaturated conditions using graphene liquid cell transmission electron microscopy. We demonstrate that the mineralization process has three steps: nucleation, diffusion-limited growth, and Ostwald ripening/coalescence. In addition, we show that the polymorphs precipitate in a specific order, from metastable aragonite to stable calcite, thus proving Ostwald’s rule of stages. In highly supersaturated solutions, the aragonite phase crystallizes in a stable manner, in addition to the calcite phase.

Understanding of lithium polysulfide (Li-PS) formation and the shuttle phenomenon is essential for practical application of the lithium/sulfur (Li/S) cell, which has superior theoretical specific energy (2600 Wh/kg). However, it suffers from the lack of direct observation on behaviors of soluble Li-PS in liquid electrolytes. Using in situ graphene liquid cell electron microscopy, we have visualized formation and diffusion of Li-PS simultaneous with morphological and phase evolutions of sulfur nanoparticles during lithiation. We found that the morphological changes and Li-PS diffusion are retarded by ionic liquid (IL) addition into electrolyte. Chronoamperometric shuttle current measurement confirms that IL addition lowers the experimental diffusion coefficient of Li-PS by 2 orders of magnitude relative to that in IL-free electrolyte and thus suppresses the Li-PS shuttle current, which accounts for better cyclability and Coulombic efficiency of the Li/S cell. This study provides significant insights into electrolyte design to inhibit the polysulfide shuttle phenomenon.

Careful modulation of surficial and interfacial properties of electrode materials is a critical factor for determining overall electrochemical characteristics. Recent studies have indicated that metal oxide nanocoating layer (such as titanium (IV) oxide (TiO2)) on metal oxide anodes (such as tin (IV) oxide (SnO2)) exhibited superior electrochemical properties, but fundamental research on the effect and role of TiO2 layer thickness has been limited. Here we have successfully conducted in-depth study on how the thickness of TiO2 overlayer on SnO2 can have significant influence in the overall parameters of electrochemistry. It is revealed that TiO2 overlayer with 12 nm shows good cycle retention (75.8%) even after 80 cycles and retains capacity of 438.3 mAh g−1 even at high current density (5000 mA g−1). Surprisingly, it was further discovered that TiO2 layer not only alleviates the volume expansion but also helps to facilitate Li ion transport compared with SnO2. The improvements in both ionic and electrical conductivity of TiO2 layer are main factors in better cycle retention and rate capabilities. Finally, in situ transmission electron microscopy analysis was adopted to observe the growth dynamics of solid electrolyte interphase layer on TiO2@SnO2, which demonstrates that TiO2 overlayer results in homogeneous and thinner interphase layer compared with SnO2 NTs.

The conversion reaction is important in lithium-ion batteries because it governs the overall battery performance, such as initial Coulombic efficiency, capacity retention, and rate capability. Here, we have demonstrated in situ observation of the complete conversion reaction and agglomeration of nanoparticles (NPs) upon lithiation by using graphene liquid cell transmission electron microscopy. The observation reveals that the Sn NPs are nucleated from the surface of SnO2, followed by merging with each other. We demonstrate that the agglomeration has a stepwise process, including rotation of a NP, formation of necks, and subsequent merging of individual NPs.

The stress inevitably imposed during electrochemical reactions is expected to fundamentally affect the electrochemistry, phase behavior and morphology of electrodes in service. Here, we show a strong stress-composition coupling in lithium binary alloys during the lithiation of tin-tin oxide core-shell nanoparticles. Using in situ graphene liquid cell electron microscopy imaging, we visualise the generation of a non-uniform composition field in the nanoparticles during lithiation. Stress models based on density functional theory calculations show that the composition gradient is proportional to the applied stress. Based on this coupling, we demonstrate that we can directionally control the lithium distribution by applying different stresses to lithium alloy materials. Our results provide insights into stress-lithium electrochemistry coupling at the nanoscale and suggest potential applications of lithium alloy nanoparticles., Electrochemical reactions can generate stresses that detrimentally affect battery electrodes. Here, the authors directly image the lithiation of core-shell tin-based nanoparticles and show that lithium can be redistributed by applying stress and change the nanoparticle composition.

In this work, we introduce the preparation of graphene liquid cells (GLCs), encapsulating both electrode materials and organic liquid electrolytes between two graphene sheets, and the facile synthesis of one-dimensional nanostructures using electrospinning. The GLC enables in situ transmission electron microscopy (TEM) for the lithiation dynamics of electrode materials. The in situ GLC-TEM using an electron beam for both imaging and lithiation can utilize not only realistic battery electrolytes, but also the high-resolution imaging of various morphological, phase, and interfacial transitions.

We report on the fabrication of a siloxane-encapsulated quantum dot (QD) film (QD-silox film), which exhibits stable emission intensity for over 1 month even at elevated temperature and humidity. QD-silox films are solidified via free radical addition reaction between oligosiloxane resin and ligand molecules on QDs. We prepare the QD-oligosiloxane resin by sol-gel condensation reaction of silane precursors with QDs blended in the precursor solution, forgoing ligand-exchange of QDs. The resulting QD-oligosiloxane resin remains optically clear after 40 days of storage, in contrast to other QD-containing resins which turn turbid and ultimately form sediments. QDs also disperse uniformly in the QD-silox film, whose photoluminescence (PL) quantum yield (QY) remains nearly unaltered under harsh conditions; for example, 85 °C/5% relative humidity (RH), 85 °C/85% RH, strongly acidic, and strongly basic environments for 40 days. The QD-silox film appears to remain equally emissive even after being immersed into boiling water (100 °C). Interestingly, the PL QY of the QD-silox film noticeably increases when the film is exposed to a moist environment, which opens a new, facile avenue to curing dimmed QD-containing films. Given its excellent stability, we envision that the QD-silox film is best suited in display applications, particularly as a PL-type down-conversion layer.

Formation of stable solid electrolyte interphase (SEI) layer is critical to outstanding performance of energy storage devices, because it acts as a passive layer that allows facile transport of ions but forbids electron transport between the electrolyte and electrode. Although much study has been devoted to investigate the morphology and structure of SEI layer using a myriad of analytical devices on past decades, the direct observation of SEI layer on a real time scale has remained as a formidable challenge. In addition, it has been difficult to observe both the decomposition of electrolytes and formation process of stable SEI layer at nanometer scale. Here we utilize in situ transmission electron microscopy (TEM) using graphene liquid cell (GLC) to realize the observation of stable SEI layer formation in a sequential time scale. Upon e− beam irradiation, Li salts in the electrolytes react with reduced electrolytes and form gel-like agglomerates, which are deposited on the surface of the active material as a passivation layer and later stabilized to become more uniform in overall thickness. Additionally, growth dynamics of stable SEI layer were suggested, where the deposition of decomposed electrolytes eventually result in relatively uniform SEI layer. This paper demonstrates that it is possible to observe not only the formation of non-crystalline SEI layer but also the movement of decomposed electrolytes onto the surface of active materials which account for broader understanding of SEI layer, and has the potential to detect important interfacial phenomena in electrochemical devices that were overlooked so far.

We trace Sn nanoparticles (NPs) produced from SnO2 nanotubes (NTs) during lithiation initialized by high energy e-beam irradiation. The growth dynamics of Sn NPs is visualized in liquid electrolytes by graphene liquid cell transmission electron microscopy. The observation reveals that Sn NPs grow on the surface of SnO2 NTs via coalescence and the final shape of agglomerated NPs is governed by surface energy of the Sn NPs and the interfacial energy between Sn NPs and SnO2 NTs. Our result will likely benefit more rational material design of the ideal interface for facile ion insertion.

Sodium ion batteries have been considered a promising alternative to lithium ion batteries for large-scale energy storage owing to their low cost and high natural abundance. However, the commercialization of this device is hindered by the lack of suitable anodes with an optimized morphology that ensure high capacity and cycling stability of a battery. Here, we not only demonstrate that copper sulfide nanoplates exhibit close-to-theoretical capacity (~560 mAh g–1) and long-term cyclability, but also reveal that their sodiation follows a non-equilibrium reaction route, which involves successive crystallographic tuning. By employing in situ transmission electron microscopy, we examine the atomic structures of four distinct sodiation phases of copper sulfide nanoplates including a metastable phase and discover that the discharge profile of copper sulfide directly reflects the observed phase evolutions. Our work provides detailed insight into the sodiation process of the high-performance intercalation–conversion anode material., Copper sulfide allows for high-performance sodium ion storage, yet its sodiation mechanism is poorly understood. Here, the authors examine the atomic structures of sodiated phases via in situ transmission electron microscopy, showing a non-equilibrium reaction pathway.

The conversion reaction is important in lithium-ion batteries because it governs the overall battery performance, such as initial Coulombic efficiency, capacity retention, and rate capability. Here, we have demonstrated in situ observation of the complete conversion reaction and agglomeration of nanoparticles (NPs) upon lithiation by using graphene liquid cell transmission electron microscopy. The observation reveals that the Sn NPs are nucleated from the surface of SnO2, followed by merging with each other. We demonstrate that the agglomeration has a stepwise process, including rotation of a NP, formation of necks, and subsequent merging of individual NPs.

연구배경 : 호흡곤란은 호흡기질환 환자의 가장 흔한 주소이나 이를 감지하는 정확한 기전은 아직 잘 알려져 있지 않다. 폐질환에서 호흡곤란의 심한 정도와 치료에 대한 반응을 측정하는 데 있어 객관적인 폐기능을 이용하여 왔으나 호흡곤란은 폐 환기능 뿐 아니라 심장, 폐질환, 심인적 요인 등을 반영한 복합적인 증상이므로 주관적으로 측정하는 호흡곤란지수(dyspnea index)를 사용하여 이러한 증상의 정도를 양적으로 측정하는 것도 유용할 것으로 생각된다. 방법 : 증상이 기관지천식 환자를 대상으로 Visual Analogue Scale(VAS) 및 Borg Scale Dyspnea Index (BSDI)와 Spirometry를 검사전 휴식상태, methacholine 유발검사에서 양성을 나타내었을 때, 기관지확장제 투여후 각각 측정하였다. 결과 : 1) 기저상태와 Methacholine 및 기관지확장제 투여후 시행한 폐기능검사 결과와 VAS 및 BSDI 간 상관관계는 없었다. 2) FEV1, FVC 및 MMFR 변화량과 VAS 및 BSDI 변화량 간에도 상관관계는 없었다. 3) 천식의 증상호소가 경미한 환자군이 증상호소가 심한 환자군 보다 methacholine 및 기관지확장제 투여 후의 VAS 및 BSDI의 변화가 더 컸다. 4) 호흡곤란지수중 VAS이 BSDI 보다 조금 큰 수치 및 변화량을 보였으며 두 지수 간의 상관관계를 볼 수 있었다(R=0.82). 결론 : 기관지천식 환자에서 기저상태 및 Methacholine 유발검사시에 객관적인 폐기능 검사 수치의 유의한 차이가 없음에도 불구하고 주관적인 호흡곤란지수는 변화하는 경향을 보였으며, 이는 경중 천식군에서 더욱 뚜렷하였다. 호흡곤란지수는 환자 간의 비교척도로는 사용될 수 없으나 한 환자에서 경과관찰이나 치료효과를 판정하는데에 spirometry와 함께 중요한 지표가 될 것으로 생각된다. 【Background: Despite dyspnea is a predominant complaint of patients with respiratory disease, the mechanisms contributing to the sensation of breathlessness are poorly understood. Traditionally, physicians have measured objective pulmonary function to assess severity of dyspnea. But it will be also useful to measure subjective dyspnea index because dyspnea probably depends on a complex interplay of mechanical, experimental, emotional and other factors. Method: We measured breathlessness at rest, after Methacholine challenge and then bronchodilator inhalation using a Visual Analogue Scale (VAS) and Borg Scale Dyspnea Index (BSDI) in stable asthmatic patients. Spirometry was performed concomittently. Results: There was no correlation between dyspnea index and FEV1. There was also no correlation between the change in dyspnea index and change in FEV1. The change in dyspnea index after methacholine and bronchodilator was greater in clinically mild asthmatic patients than clinically severe symptomatic group. Conclusion: In asthmatic patients, there was a wide variation in sensory response for any given FEV1, and the change in perception of dyspnea was greater in those with clinically mild symptoms. The measurement of dyspnea index may yield information complementary to that obtained by spirometry.】