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At least 1,027 records · Page 57

Local Modulation of Single-Atomic Mn Sites for Enhanced Ambient Ammonia Electrosynthesis

Rationally tuning the local structures of single-atomic active sites for the electrocatalytic N 2 reduction reaction (NRR) remains an urgent but worthwhile research topic. Herein, we accomplish the local modulation of single-atomic Mn sites and construct single Mn–O 3 N 1 sites anchored on porous carbon (Mn–O 3 N 1 /PC) by delicately controlling the Mn–O bonding conditions. Furthermore, the constructed structures are confirmed via the combination of atomic-scale imaging, Raman spectroscopy, synchrotron radiation-based soft and hard X-ray absorption spectroscopies, and X-ray photoelectron spectroscopy. The Mn–O 3 N 1 /PC catalyst yields an NH 3 yield rate of 66.41 μg h –1 mg cat. –1 (corresponding to 1.56 mg h –1 mg Mn –1 ) at -0.35 V versus reversible hydrogen electrode, which is about four times that on the control Mn–N 4 /PC catalyst. The enhanced NRR performance is ascribed to its unique geometry and electronic structures, which not only facilitate the adsorption and activation of the N 2 molecule but also lower the free energy change of the potential-determining step.

36 MATERIALS SCIENCE↗

Real-time interface investigation on degradation mechanism of organic light-emitting diode by in-operando X-ray spectroscopies

Understanding the chemical evolution at the interface of organic light-emitting diodes (OLEDs) under working conditions is critical for addressing device failure and further improving performance. In this work, an in-operando approach was developed employing synchrotron-based X-ray absorption spectroscopy (XAS) to investigate the electronic structures and chemical degradation mechanisms of a model tris(8-hydroxyquinoline) aluminum (Alq 3 )-based OLED device under working condition. The results identify that Mg atoms from the electrode migrate into the Alq 3 organic layer under a potential bias and replace Al atom sites, forming the unstable Mgq 3 species which lead to device degradation. Here, the findings from the classic and simple model device elucidate the degradation mechanisms occurred at the interface of OLED devices, which may facilitate the development of more efficient and stable OLED devices with complex structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intermediate Sr 2 Co 1.5 Fe 0.5 O 6-δ Tetragonal Structure between Perovskite and Brownmillerite as a Model Catalyst with Layered Oxygen Deficiency for Enhanced Electrochemical Water Oxidation

The generation of hydrogen in an environmentally benign way is highly essential to meet future energy demands. However, in the process of splitting water electrochemically, sluggish kinetics of the oxygen evolution reaction (OER) curtails its applicability, as it drags energy input. Herein, we synthesized SrCo-Fe-O oxides to optimize their OER activity by varying the Co/Fe ratio. Among them, Sr 2 Co 1.5 Fe 0.5 O 6-δ exhibited the best OER catalytic activity in the series, with an overpotential of 318 mV at 10 mA cm -2 and Tafel slope of 44.8 mV dec -1 . High-resolution neutron powder diffraction analysis identified an intermediate structure between the perovskite and brownmillerite, with alternating layers of disorderly orientated oxygen-deficient tetrahedra and fully stoichiometric octahedra. The unique stacking of tetrahedral and octahedral units facilitates desired interactions between the electrode surface and electrolyte. Theoretical calculations revealed that increased covalency of Co 3d and O 2p in Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide is another primary contributor to its augmented water oxidation ability. As a model for developing catalysts with such an intermediate structure, the synergetic effect of oxygen vacancy and hybridization between Co 3d and O 2p assured the Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide as a better catalyst for its enhanced OER activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimizing high energy density sulfur cathodes: A multivariate approach to electrode formulation and processing

Lithium-sulfur (Li-S) batteries involve complex solid-liquid-solid phase transformations during both discharging and charging processes, where cathode materials, formulation, and structure play a crucial role. Here, a design of experiments (DoE) methodology and an empirical model are developed to systematically explore the interactions and trade-offs among cathode factors and process variables, and to obtain generalizable effects estimates for the multivariate system. Compared to the conventional one-factor-at-a-time (OFAT) approach, this work demonstrates advantages in both efficiency and accuracy by allowing the data to guide future research and decisions. Further, an optimized cathode formulation and processing parameters are predicted and validated experimentally, achieving over 1000 mAh g -1 in discharge capacity and improved cycling under practical lean electrolyte (4 µL mg -1 S) and high S-loading cathodes (>4 mg cm -2 ) conditions. The optimized cathode was scaled up and assembled into Li-S pouch cells, achieving 316 Wh kg -1 in cell-level energy, proving that the comprehensive and rigorous framework for optimizing complex systems with DoE leads to improved performance in a practical pouch cell system.

25 ENERGY STORAGE↗

Electrochemistry-Induced Restructuring of Tin-Doped Indium Oxide Nanocrystal Films of Relevance to CO 2 Reduction

The electrochemical reduction of CO 2 into fuels using renewable electricity presents an opportunity to utilize captured CO 2 . Electrocatalyst development has been a primary focus of research in this area. This is especially true at the nanoscale, where researchers have focused on understanding nanostructure-property relationships. However, electrocatalyst structure may evolve during operation. Indium- and tin-based oxides have been widely studied as electrocatalysts for CO 2 reduction to formate, but evolution of these catalysts during operation is not well-characterized. Here, we report the evolution of nanoscale structure of precise tin-doped indium oxide nanocrystals under CO 2 reduction conditions. We show that sparse monolayer nanocrystal films desorb from the electrode upon charging, but thicker nanocrystal films remain, likely due to an increased number of physical contacts. Upon applying a cathodic voltage of –1.0 V vs RHE or greater, the original 10-nm diameter nanocrystals are no longer visible, and instead form a larger microstructural network. Elemental analysis suggests the network is an oxygen-deficient indium-tin metal alloy. We hypothesize that this morphological evolution is the result of nanocrystal sintering due to oxide reduction. Furthermore, these data provide insights into the morphological evolution of tin-doped indium oxide nanocrystal electrocatalysts under reducing conditions and highlight the importance of post-electrochemical structural characterization of electrocatalysts.

25 ENERGY STORAGE↗

Doping Scheme in Atomic Chain Electronics

Due to the dramatic reduction in MOS size, there appear many unwanted effects. In these small devices, the number of dopant atoms in the channel is not macroscopic and electrons may suffer significantly different scattering from device to device since the spatial distribution of dopant atoms is no longer regarded as continuous. This prohibits integration, while it is impossible to control such dopant positions within atomic scale. A fundamental solution is to create electronics with simple but atomically precise structures, which could be fabricated with recent atom manipulation technology. All the constituent atoms are placed as planned, and then the device characteristics are deviation-free, which is mandatory for integration. Atomic chain electronics belongs to this category. Foreign atom chains or arrays form devices, and they are placed on the atomically flat substrate surface. We can design the band structure and the resultant Fermi energy of these structures by manipulating the lattice constant. Using the tight-binding theory with universal parameters, it has been predicted that isolated Si chains and arrays are metallic, Mg chains are insulating, and Mg arrays have metallic and insulating phases [1]. The transport properties along a metallic chain have been studied, emphasizing the role of the contact to electrodes [2]. For electronic applications, it is essential to establish a method to dope a semiconducting chain, which is to control the Fermi energy position without altering the original band structure. If we replace some of the chain atoms with dopant atoms randomly, the electrons will see random potential along die chain and will be localized strongly in space (Anderson localization). However, if we replace periodically, although the electrons can spread over the chain, there will generally appear new bands and band gaps reflecting the new periodicity of dopant atoms. This will change the original band structure significantly. In order to overcome this dilemma, we may place a dopant atom beside the chain at every N lattice periods (N > 1). Because of the periodic arrangement of pant atoms, we can avoid the unwanted Anderson localization. Moreover, since the dopant atoms do not constitute the chain, the overlap interaction between them is minimized, and the band structure modification can be made smallest. Some tight-binding results will be discussed to demonstrate the present idea.

Toshishige, Yamada↗

Prospects for Employing Lithium Copper Phosphates as High-Voltage Li-Ion Cathodes

Three compositions of lithium copper phosphates: Li 2 CuPO 4 , Li 2 Cu 5 (PO 4 ) 4 , and Li 2 CuP 2 O 7 have been studied as potential high-voltage cathode materials for Li-ion batteries, following computational predictions of high operating voltages. An assisted-microwave preparation of Li 2 CuPO 4 , which is otherwise difficult to prepare in nearly pure form, has been developed. The electrochemical performance of all three compounds has been investigated. Additionally, the cyclability of these materials is found to be poor due to structural changes, irreversible reduction to metallic copper at potentials as high as 2.5 V, and the possibility of dissolution into the electrolyte. Some general understanding in regard to the use of Cu compounds in redox electrodes is presented.

25 ENERGY STORAGE↗

Liquid Phase Exfoliation of Chemically Prelithiated Bilayered Vanadium Oxide in Aqueous Media for Li-Ion Batteries

Bilayered vanadium oxides are attractive for energy storage due to their high initial specific capacities, which could be stabilized by integrating the bilayers with conductive nanoflakes often produced in a form of aqueous dispersions. Therefore, exfoliation of the bilayered vanadium oxides in water with high yield is desirable. Here, this work introduces the first aqueous exfoliation of chemically prelithiated bilayered vanadium oxide (i.e., δ-Li x V 2 O 5 ·nH 2 O or LVO) followed by vacuum filtration to produce a free-standing film, exhibiting a lamellar stacking of the bilayered vanadium oxide nanoflakes as evidenced by scanning electron microscopy. Due to the hydrated nature of bilayered vanadium oxides, the relationship between interlayer water content and the vacuum drying temperature (105 °C vs 200 °C) was studied using X-ray diffraction, thermogravimetric analysis, and Raman spectroscopy. It was found that vacuum drying the LVO nanoflakes at 200 °C enabled more efficient removal of crystallographic water than drying at 105 °C, and did not induce a phase transformation. Scanning transmission electron microscopy confirmed the layered structure of the samples, which was more well-ordered in the 200 °C case and had no clear boundaries between flakes at the atomic scale. Furthermore, electrochemical testing in nonaqueous Li-ion cells revealed that vacuum drying at 200 °C led to improvements in ion storage capacity and electrochemical stability. Improvements in electrochemical charge storage properties of the electrodes obtained via LVO exfoliation and free-standing film assembly in water dried at 200 °C reveal that conventional battery electrode drying protocols need to be revised as new electrochemically active materials are synthesized, such as hydrated layered oxides with expanded interlayer regions. The remaining capacity fading can be attributed to the structural LVO degradation, dissolution of vanadium oxide in electrolyte, and parasitic effects of the remaining interlayer water molecules. Our results establish an environmentally friendly and safe approach to obtain two-dimensional (2D) bilayered vanadium oxide nanoflakes and create a pathway to constructing novel 2D heterostructures for improved performance in energy storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recent Progress in Electrochemical Nitrogen Reduction on Transition Metal Nitrides

Distributed electrochemical nitrogen reduction reaction (ENRR) powered by renewable energy for the on-site production of ammonia is an attractive alternative to the industrial Haber–Bosch process, which is responsible for roughly 2 % of global energy consumption. Here, in this Review, we summarize recent progress in the ENRR catalyzed by transition metal nitrides (TMNs). The unique electronic structures of TMNs make them promising ENRR catalysts for active and selective ammonia production, which have been predicted theoretically and demonstrated experimentally. Reaction pathways and deactivation mechanisms of the ENRR on different TMNs are surveyed, and current understanding of structure-activity relations is discussed. To develop highly active, selective, and stable TMN catalysts for industrial-scale ENRR, membrane electrode assembly configuration is recommended in catalyst evaluation. Furthermore, we highlight the importance of developing mechanistic understanding on ENRR with different operando spectroscopic techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

(CrMnCoNiZn) 3 O 4 @PPy core-shell nanocomposite with excellent electrochemical performance as lithium-ion battery anode

High entropy oxides (HEOs) have an excellent potential for use as electrode materials in lithium-ion batteries (LIBs) due to their high theoretical specific capacity. In this work, spinel-structured (CrMnCoNiZn) 3 O 4 HEO nanoparticles with five elements in equal molar ratio is first generated by solution combustion method. (CrMnCoNiZn) 3 O 4 @polypyrrole (PPy) nanocomposites are prepared by in-situ polymerization method. As an anode for lithium-ion batteries, the electrochemical performance of the (CrMnCoNiZn) 3 O 4 @PPy composite outperforms that of (CrMnCoNiZn) 3 O 4 nanoparticles. The capacity is 802 mAh/g after 100 cycles at a current density of 100 mA/g, 416 mAh/g after 1000 cycles at a high current density of 1 A/g, and 360 mAh/g rate capacity at 2 A/g. The excellent electrochemical performance of the composites is mainly due to the fact that the conductive and flexible PPy is encapsulated on the high-entropy oxides, which can alleviate the volume change triggered by extraction-insertion of lithium ions process, as well as enhance the electrical conductivity and reduce the occurrence of some side reactions. Finally, this method of compositing materials can also be used in other HEOs and conductive polymers, providing a new idea to enhance the electrochemical properties of HEOs.

25 ENERGY STORAGE↗

Capacitive deionization using carbon derived from an array of zeolitic-imidazolate frameworks

Capacitive deionization (CDI) represents one of the most thermodynamically efficient technologies for brackish water desalination. Its performance is highly reliant on the surface properties of carbon-based electrodes. Zeolitic-imidazolate framework (ZIF)-derived carbon materials have emerged among the most promising candidates owing to their high structural and compositional tuneability. However, the impacts of the precursory ZIF structure on the properties of the final carbon, and therefore, CDI capacity and efficiency remain to be further explored. In this work, four Zn-based ZIFs with different side-chain substitutions on the imidazolates were synthesized on a gram scale with high yields to produce N-doped carbons by pyrolysis. Next, the resulting carbons along with four commercial carbon blacks were characterized physically and electrochemically to explore the structure-performance relationship. We demonstrated that the imidazole side-chain substitution alters the ZIF's decomposition during pyrolysis, influencing the elemental compositions, surface properties, wettability and graphitization levels. The diverse carbon properties result in variable double layer capacitance and charge-transfer resistance, ultimately impacting the CDI performance. Among these carbons, Zn (4abIm)2-C afforded the greatest salt adsorption capacity of 14.19 mg NaCl $·g_C^{–1}$, while Zn (mIm) 2 -C showed the highest overall salt adsorption capacity and rate; both exceeded the performance of the commercial carbon blacks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deciphering volume changes in Li-S solid-state battery components during cycling: Implication for advanced battery design

Here, in this work, we developed custom fixtures to investigate the mechanical and electrochemical behavior of all-solid-state lithium batteries during cycling under constant pressure and constant volume conditions. We successfully monitored vertical displacements during constant pressure cycling and pressure variations during constant volume cycling, allowing us decouple volume changes in the sulfur, Li 2 S cathodes, LixIn anode, and solid-state electrolyte. Scanning electron microscopy and electrochemical impedance spectroscopy confirmed that two structural changes occur during ASSLB cycling: (1) irreversible fractures in the active material particles, and (2) void formation within the electrode matrix. While the fractures in primary particles are permanent, void formation can be mitigated through stack pressure, which promotes particle rearrangement in the electrode matrix. Our findings emphasize the importance of stack pressure in maintaining the microscale integrity of all-solid-state lithium batteries, preventing void formation and enhance battery performance and durability.

Cell Design↗

Alizarin Multilayers Adsorbed onto Glassy Carbon Electrodes for Electrochemical Sequestration of Manganese, Sodium, and Lithium Cations

The development of efficient methods for metal ion recovery and water remediation is critical for addressing the nation’s urgent need for secure domestic supply chains, overcoming critical materials challenges, and ensuring resilient manufacturing. Here, we present a novel approach for synthesizing stable Alizarin (Alz, 1,2-dihydroxy anthraquinone) multilayers on glassy carbon electrodes (GCEs) for electrochemical sequestration of manganese, sodium, and lithium cations. Alz-GCEs exhibit negatively shifted reduction potentials, indicating strong interactions between Alz and metal cations through metal-coupled electron transfer (MCET) mechanisms. The cation binding interactions and redox behavior of these electrodes were investigated using cyclic voltammetry (CV) and density functional theory (DFT) calculations. Our results demonstrate that Alz forms multilayer structures on GCEs with redox properties that are modulated by the presence of metal cations in the electrolyte. DFT calculations provide insights into the electrochemical mechanism, indicating both stepwise and concerted pathways for metal binding. The findings highlight the potential of Alz-GCEs for efficient and selective metal ion capture, which could be useful for developing sustainable materials for critical metal recovery and water remediation. This work suggests that redox-mediated organic adlayers are promising candidates for advancing electrochemical separation technologies of metal ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemically Assisted Single Crystal Growth of Reduced Preyssler Polyoxometalates Decorated with M 2+ ( M = Co, Ni) and Cubane–Like Ni 4 O 4 Units

Polyoxometalates (POMs) are of great interest to the scientific community, and their reduction and nucleation have been well–established by multi–step techniques. The present study develops an electrochemical approach for simultaneous reduction and nucleation of polyoxometalate–containing solids. Herein we report crystal growth of reduced Preyssler polyoxotungstate–based (anionic formula [NaP 5 W 30 O 110 ] 14– ) new crystalline solids made of Preyssler anions interlinked by Co 2+ and Ni 2+ ions. Crystal nucleation and in situ reduction were achieved at room temperature using a two silver wire electrode setup in various aqueous solutions under constant applied potentials. The POM material was deposited on the cathode, and its structure was characterized by X–ray diffraction techniques. The primary structure type observed involves POMs decorated by disordered Co 2+ /Ni 2+ octahedra and fused into 1–D pillars by additional Co 2+ /Ni 2+ octahedra. Additionally, a secondary phase was observed in the Ni–based reactions, where reduced Preyssler anions are decorated by Ni 4 O 4 cubane–like units. To understand the electrochemical process, polarization curves of the electrolyte solutions are presented, suggesting an applied potential best suited for crystal growth. The work highlights the effectiveness of an electrochemical pathway where nucleation and simultaneous reduction of POMs can make novel reduced POM solids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stabilizing Dendritic Electrodeposition by Limiting Spatial Dimensions in Nanostructured Electrolytes.

The tendency of metals to form uncontrolled dendritic morphologies during electrodeposition hinders the development of safe and reliable metal batteries. Multiphase nanostructured electrolytes can suppress dendritic growth if the mechanical modulus of the electrolyte is high relative to that of the metal or if the conducting channels are confined to nanoscale dimensions. Direct visualization and analysis of electrodeposition within polymeric nanostructures elucidates the structure-property relationships and mechanisms underlying the suppression of dendrite growth. Here, we fabricate precisely structured multiphase films composed of nanochannels of a polymeric electrolyte in a background of nonconductive polymer on top of coplanar electrodes. The devices enable imaging and analysis of electrodeposition behavior as a function of channel width by scanning electron microscopy. We find that electrodeposition is confined to individual conductive channels and that radial propagation of the dendritic morphology is suppressed in channels for which the width is smaller than the characteristic dendritic nucleation size.

Sharon, Daniel↗

Metallic and porous Ti nanorod arrays for visible-IR light absorption and dendrite-free stable lithium-metal batteries

It is still a challenging task to prepare highly porous nanorod arrays of metals formed on substrates for optical and energy storage applications. Herein, we demonstrate the design and synthesis of black color, metallic and highly porous Ti nanorod arrays as novel current collectors for dendrite-free and highly stable Li-metal anodes. The high porosity of metallic nanorod arrays provides numerous heterogeneous nucleation sites and huge contact area and large space for the accommodation of Li metal. The conductive metallic Ti nanorod arrays enhance electrode integration. Effectively, it eliminates formation Li dendrites and demonstrates superior cycling stability over 300 cycles. Additionally, the unique porous structures of the nanorod arrays can decrease the amplitude of forced vibration in narrow space leading to light absorption. Interestingly, the metal is black instead of metallic color. The black metallic nanorod arrays can absorb more than 96% of both visible and infra-red lights. Furthermore, this black color metallic porous nanorod arrays may find additional applications in aerospace, energy, biomedical, defence, and chemical industries.

25 ENERGY STORAGE↗

Effect of sinter fracture and ohmic resistance on capacity retention in the nickel oxide electrode

The lifetime of batteries which utilize the nickel oxide electrode is often limited because this electrode loses a significant portion of its capacity as it is cycled. It is asserted that this capacity loss may often be attributed to cracking or separation of the conductive nickel sinter in the electrode, which forces electronic current to pass through the poorly conducting hydrated oxide and thus imposes a significant ohmic resistance. The model indicates that the oxide develops a nearly insulating layer which prevents complete discharge in the cycled electrode at usable rates. The capacity retention can be improved by reducing the cyclic stresses or strengthening the current collecting structure, redistributing it to provide a shorter current path through the solid phase, or by increasing the conductivity of the oxide to delay the formation of an insulating layer.

Lanzi, Oscar↗