bluuebunny/crossref_metadata_2025 huggingface dataset:
Advancements in Additive Manufacturing of Protonic Ceramic Fuel Cells
Authors: Asghar Muhammad Imran
Published: February 2024

Protonic ceramic fuel cells (PCFCs), also known as proton conducting solid oxide fuel cells, are a promising low-temperature (400-600oC) fuel cell technology. Compared to conventional oxygen-ion conducting ceramic materials, proton conducting ceramic electrolyte materials have lower activation energy (< 50 eV), which can enhance fuel cell efficiency and power output. Additive manufacturing has the potential to revolutionize PCFC manufacturing, as it enables fabrication of both dense and porous structures with desirable mechanical and electrochemical properties. In this study, we employed extrusion-based 3D printing to fabricate PCFCs using BaZr0.3Ce0.5Y0.15O3-δ and BaZr0.4Ce0.4Y0.1Yb0.1O3-δ as electrolytes, NiO as anode, and BaCo0.4Fe0.4Zr0.1Y0.1O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ as cathode. For comparison, we also printed oxide conducting ceramic fuel cells using gadolinium-doped-ceria (GDC ) as electrolyte. We investigated the printable pastes' rheological properties using dynamic light scattering, viscometer, tensiometry, differential scanning calorimetry, and thermal gravimetric analysis. We also characterized the cells using current-voltage measurements, electrochemical impedance spectroscopy, and various spectroscopic and microscopic techniques (HR-TEM-EELS, SEM-EDX) to understand the underlying mechanisms. Finally, we conducted a systematic study to optimize the sintering temperature for optimal fuel cell performance and investigate degradation mechanisms to improve stability.
(Invited) Development of Thin-Film Solid Oxide Cells for Power Generation and Hydrogen Production
Authors: Minh Nguyen Q.
Published: February 2024

Thin-film solid oxide cells (TF-SOCs) fabricated by sputtering have been developed for power generation and hydrogen production applications. TF-SOCs have been considered for cell configuration in this development because of the potential for efficient operation at reduced temperatures (≤700oC). Reduced temperature operation allows a wider choice of cell and ancillary materials, minimizes elemental migration/interaction, and reduces thermal stresses, thus improving cell reliability and durability. Sputtering has been considered for fabrication of TF-SOCs because the technique can create dense or porous films as required for the cell components. In addition, a fabrication process based on sputtering is readily scaled to large cell sizes and large volume production. All-sputtered TF-SOC cells have been shown to exhibit exceptionally high performance in both power generation and electrolysis modes, for example, a peak power density of 2.7W/cm2 (fuel cell mode) and a current density of 2.6A/cm2 at 1.3V (electrolysis mode) at 650oC with 50%H2-50%H2O. TF-SOC cells as large as 15 cm x 15 cm size have been fabricated by sputtering. This paper discusses the development of the sputtering process for making TF-SOCs and evaluation of cell performance characteristics in power generation and hydrogen production operating modes.
(Digital Presentation) Fabrication and Characterization of 4Sc4YSZ/LSM-4Sc4YSZ Novel Electrode-Supported Half-Cell Composition for Solid Oxide Electrochemical Cells
Authors: Diamansil Pearl Jamela , Cervera Rinlee
Published: February 2024

Scandium and Yttrium co-doped ZrO2 (4Sc4YSZ) thin film solid electrolyte has exhibited improved conductivities and phase stability by considering advantages of both Y-doped zirconia (YSZ) and Sc-doped zirconia (ScSZ). To further investigate the promising properties of this co-doped composition, a solid electrolyte thin film of 4Sc4YSZ deposited on a new LSM-4Sc4YSZ composite electrode was conducted. In this study, the effect of pre-sintering temperature (1000°C, 1150°C, and 1300°C) of the LSM-4Sc4YSZ electrode substrate in the deposition of a dense solid electrolyte film was studied. X-ray diffraction (XRD) analysis of all the LSM-4Sc4YSZ composite electrodes revealed distinct phases of rhombohedral LSM and cubic 4Sc4YSZ. Also, the thin film electrolytes exhibited cubic 4Sc4YSZ with calculated lattice parameters of a equal to 5.10 Å, 5.10 Å, and 5.09 Å deposited on the electrode substrate pre-sintered at 1000°C, 1150°C, and 1300°C, respectively. The obtained lattice parameters were comparable with the reference LSM (PDF card no. 000-053-0058) and 4Sc4YSZ (PDF card no. 01-080-4524). Morphological characterization via scanning electron microscopy (SEM) showed that the thin film solid electrolyte with LSM-4Sc4YSZ electrode pre-sintered at 1300°C has a relatively dense microstructure than those with lower pre-sintering electrode temperatures. In addition, the thin film deposited on the 1300°C LSM-4Sc4YSZ obtained the lowest average thickness of 12.81 µm as compared to the 1000°C and 1150°C LSM-4Sc4YSZ with thickness values of 38.32 µm and 27.99 µm, respectively. The electrochemical performance of the fabricated half-cell was analyzed using electrochemical impedance spectroscopy (EIS). The total conductivity, as calculated from the EIS results, of 4Sc4YSZ/LSM-4Sc4YSZ half-cell pre-sintered at 1300°C is 0.0726 S/cm at 700°C under oxygen gas flow environment.
Enabling Improved Electrochemical Performance of Lithium Metal Batteries with Fluorinated SO2 Based Nonflammable Inorganic Electrolyte
Authors: Choi Seong Hoon , Lee Jiwhan , Mun Seung Do , Hwang Jun Ho , Kim Hansu
Published: February 2024

Lithium metal anodes are one of the most promising candidates to replace conventional graphite anodes and achieve high energy density because of their high theoretical capacity (3,860 mAh g-1) and the low redox potential (-3.04 V versus standard hydrogen electrode). Unfortunately, the poor cycle performance and safety issues, mainly caused by the formation of lithium dendritic growth during battery cycling, hinder their practical applications. Herein, we introduce lithium metal batteries(LMBs) with fluorinated SO2 based inorganic electrolyte, LiAlCl4-xFx-3SO2. The LiAlCl4-xFx-3SO2 electrolyte exhibits nonflammability and high ionic conductivity (about 80 mS cm-1 at room temperature). In addition, we confirm that LiAlCl4-xFx-3SO2 electrolyte shows much improved cycle performance and rate capability than that of LiAlCl4-3SO2 electrolyte. It could be ascribed to the formation of more stable solid electrolyte interphase induced by the existence of AlCl3F- in LiAlCl4-xFx-3SO2. Detailed mechanism of our battery system with fluorinated SO2 based nonflammable inorganic electrolyte will be discussed in the presentation.
Structural Characterization and Electrochemical Performance of Spinel Oxide Cathodes for High Voltage Mg-Ion Batteries
Authors: Wang Evelyna , Uppuluri Ritesh , Kwon Bob Jin , Sarnello Erik , Lapidus Saul , Key Baris
Published: February 2024

Non-aqueous Mg-ion batteries are a class of next generation batteries that promise high energy densities as an alternative to Li-ion batteries. Materials discovery and development is therefore required to fulfill this promise. MgCrMnO4 solid-solution oxide spinel with suitable redox voltages and facile Mg2+ mobility has been identified as a promising candidate for practical, high voltage cathodes in Mg-ion batteries. Here, we discuss the development of this solid-solution spinel oxide class as a cathode material, novel synthesis methods of these oxide spinels, as well as their electrochemical performance. Mg-Cr-Mn spinel oxides with varying Cr and Mn content were synthesized via conventional sol-gel methods, urea co-precipitation, and layered double hydroxide precursors. High-resolution synchrotron XRD and solid-state nuclear magnetic resonance (NMR) spectroscopy characterization along with electron microscopy indicated that different synthetic routes resulted in structural and morphological differences. This in turn lead to differences in electrochemical performance: overpotentials on charge or discharge, reversibility, and deliverable capacity. Electrochemical results in Mg-ion full cells indicate improved performance (lower overpotentials, higher reversibility, and increased capacity) for MgCrxMn2-xO4 cathodes synthesized via urea co-precipitation. To the best of our knowledge, full cells testing these Mg-Cr-Mn spinel oxide cathodes have not been previously reported.
Development of Durable Materials for Cost Effective Water Splitting
Authors: Pietras John , Oistad Brian , Qian Xin , Gopalan Srikanth , Zhong Yu , Li Wenyuan
Published: February 2024

Saint-Gobain, a global leader in ceramic and polymer based materials and components has been developing solutions for fuel and electrolysis cells for over 20 years. These solutions include; electrode and electrolyte materials, innovative cell and stack designs, ceramic interconnects, seals (both glass-ceramic and polymer based) and hot box designs. Although high temperature electrolysis promises to be an efficient solution to the production of hydrogen, durability and performance improvements are still required to produce devices that are economically feasible. A promising material family for the air electrode are rare-earth nickelate oxides with the Ruddlesden-Popper structure. These oxides are known to have a point defect structure in which oxygen interstitials play a key role in the oxygen surface exchange and transport through the lattice. Although the performance of the rare-earth nickelates can be high, they unfortunately react and decompose when in contact with rare-earth doped ceria. Ceria is typically added as a second phase from the standpoint of buffering the coefficient of thermal expansion, providing additional oxygen ionic conducting paths, and for forming the buffer layer preventing adverse reactions between the oxygen electrode and the electrolyte which are typically yttrium or scandium doped zirconia.

This work focuses on stabilizing the rare-earth nickelate electrodes through compositional modifications while developing cell-design agnostic material solutions using these materials. The driving force for nickelate decomposition was determined to be the high limits for cation solubility within typical ceria-based barrier layers. A solution to this problem is presented. In addition, towards improving the performance of cells the oxygen diffusion mechanism was modeled allowing the calculation of ionic conductivity for a variety of cation substitutions within the nickelate structure. Fundamental material properties such as exchange coefficient, oxygen incorporation into the lattice as a function of partial pressure, and electrode resistance over time were measured. Finally, an innovative processing technique for the simultaneous multilayer coating of highly loaded slurries was developed. This process provides a reduction in the number of processing steps required to produce cells while also allowing for good layer adhesion as well as thickness control at the 2.5 micron range.
Novel Current Collector for High Energy Density Lithium-Metal Batteries
Authors: Wan Mintao , Liu Haowen , Wu Nae-Lih (Nick) , Passerini Stefano , Bresser Dominic
Published: February 2024

The energy density of lithium-metal batteries (LMBs) relies to a substantial fraction on the thickness of the lithium-metal anode.1,2 Additionally, the commonly used copper current collector adds a significant mass to the electrode weight (e.g., 77% when considering a 50 μm thick lithium and 10 μm thick copper), but the thinner the lithium foil, the more important becomes the current collector to provide suitable mechanical properties and ensure a good electronic contact across the whole negative electrode.

Herein, we report the design of a novel current collector (patent application pending) that enables a substantial reduction in mass, while providing high electronic conductivity and suitable mechanical properties. Moreover, LMBs with a thin lithium foil and a Ni-rich NMC cathode comprising such new current collector reveal a superior performance compared to those containing a standard copper foil.

References

1 Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy
4, 180-186, (2019).

2 Niu, C. et al. Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries. Nat. Energy, 6, 723–732, (2021).
(Invited) A Chemical Mechanism of Carbonate Electrolyte Failure at Silicon Anode Interface for New Electrolyte Design
Authors: Woods Eliot , Wu Dezhen , Liu Haoyu , Key Baris , Vaughey John T. , Zhang Zhengcheng
Published: February 2024

Silicon (Si) anode has tremendous potential for the next-generation high energy density lithium-ion battery, but the development of devices with sufficient capacity retention and calendar life remains elusive. While numerous studies have characterized the composition and dynamics of the solid-electrolyte-interface (SEI) on silicon anodes, the chemical mechanisms that produce the identified species remain largely speculative and conflicting. In this presentation, we demonstrate the use of trimethylsilyllithium as a model compound to study the chemical mechanisms of electrolyte failure unique to silicon anodes. The insights from this mechanistic study led to the rational design of new electrolytes that outperform traditional EC-based carbonate electrolytes demonstrated in NMC811/Si full cells.
Detrimental Effects of Metal Foil’s Surface Imperfections on Metal Plating/Stripping and Facile Solutions
Authors: He Pan , Huang Jiaxing , Xu Yang
Published: February 2024

Rechargeable metal batteries have attracted great interest and are considered one of the most promising high-energy density storage systems. These devices benefit from the large specific volumetric capacities and high specific gravimetric capacities of metal anodes. Foils or sheets are the most common form of anode for metal batteries since they are massively manufactured and readily accessible. But short circuits from dendrites grown on metal foil anodes can dramatically decrease the cycling stability and lead to premature failure of the batteries.

Homogeneous metal plating/stripping is the key to avoiding dendrite formation. And the surface uniformity of metal electrodes is crucial for the initial nucleation and growth, which greatly affects the subsequent deposition. Here, we show that manufacturing-induced defects, including surface imperfections such as a roughened surface, orange peel features, microcracks, scratches, or fold lines, and unpolished edges from cutting can all promote local dendrite growth, leading to drastically decreased cycling stability of the demonstrated Zn metal batteries and K metal batteries. Polishing the metal electrodes on both sides and edges is shown to be effective to improve the electrochemical homogeneity of the metal anode and extend the cycling lifespan by over 700% in the demonstrated Zn metal cells. Finally, we demonstrate a simple and rapid surface passivation strategy that drastically increases the tolerance of such defects in Zn metal batteries. Also, we proposed a scalable, easily automated, and facile metallic K manufacturing with robust performance in K metal batteries.

Since such imperfections are ubiquitous in commercially available metal foil products. Our results remind researchers about the significant detrimental effects of these very common defects introduced by metal manufacturing and processing, which should be taken into consideration evaluating metal battery performances. Furthermore, we call for research efforts to develop effective strategies that are scalable, easily automated, and cost-effective to increase the tolerance of batteries over such defects, which will be very important for large-scale, cost-effect energy storage hubs.

References

Pan He and Jiaxing Huang. "Detrimental effects of surface imperfections and unpolished edges on the cycling stability of a zinc foil anode." ACS Energy Letters, 2021,6,1990-1995.

Pan He and Jiaxing Huang. "Chemical passivation stabilizes Zn anode." Advanced Materials, 2022, 34, 2109872.

Pan He and Yang Xu. "Facile manufacturing potassium metal anode with robust performance". In preparation.

Figure 1
Lithium Electrode Protection for Long Cycle Life and High Rate Capability Batteries
Authors: Mikhaylik Yuriy , Scordilis-Kelley Chariclea , Laramie Mike , Restrepo Carlos
Published: February 2024

Sion Power will present breakthrough technology leading to the highest combination of specific energy, cycle life and rate capability. In the core of this transformational energy storage solution is a protected metallic lithium anode with several levels of protection: physical barrier, chemical passivation of lithium surface, lithium morphology control through pressure application and optimal charge-discharge algorithms. Protected lithium anode combined with various intercalation cathodes offers wide spectra of cell designs with specific energies of 620 Wh/kg at 270 cycles to 400 Wh/kg and cycle life exceeding 2500 cycles.

The presentation will discuss Sion Power’s technology approaches, current state of energy density, rate capability and will be more focused on impact of charge-discharge algorithms on lithium morphology and cycle life.
Realizing High-Performances Sb Anodes for K-Ion Batteries
Authors: DU Xiaoqiong , Zhang Biao , Nicolosi Valeria
Published: February 2024

Alloy anodes have long been considered promising alternatives to carbon counterparts for high-energy K-ion batteries (KIBs) as they could uptake several ions per K atom through alloying reactions, delivering exceptional capacities at low voltage. However, alloy electrodes usually undergo severe volume expansion upon large K ion insertion, which will trigger the pulverization of active particles and the breakage of solid electrolyte interphase (SEI), leading to rapid capacity degradation. Instead of fabricating nanostructured materials, novel electrolyte formulations can be used to realize stable cycling of high-capacity anodes in KIBs. Sb is a promising low-cost anode material for KIBs, possessing a high theoretical capacity of 660 mAh g-1 at average voltage of about 0.5V toward K+/K. However, it shows rapid capacity degradation in conventional carbonate-based electrolytes. To stabilize the Sb anodes, novel ether-based KIB electrolytes are designed to replace the conventional ones, enabling a high reversible capacity over 180 cycles. It is found that a thinner and amorphous SEI, with abundant oligomer-like species, is built in ether base electrolytes. Such SEI is more elastic, and can effectively wrap the Sb particles to accommodate repeated volumetric changes, and preventing copious electrolytes decomposition. These findings allow us to develop crucial fundamental knowledge to design ideal SEIs for stabilizing alloy anodes to boost the energy densities of today’s alkali-metal ion batteries.
Transport Properties of Hard Carbons
Authors: Alsofi Giar
Published: February 2024

Sodium-ion batteries (SIB) have been heavily researched, as a potential replacement for Lithium ion batteries (LIB) as their components are more readily obtainable, lower cost and they have similar working principles to LIB. Hard Carbon (HC) is the current state-of-the-art anode for SIB material due to its relatively low cost, overall performance and availability. Great effort has been focused into improving and better understanding the overall mechanism of HC, which is still a subject of debate.

To better understand the mechanism of, and the obstacles to, charge transfer during charge and discharge of the cell, Hard carbon has been studied at different temperatures. The transitions between different stable and unstable phases are observed which have not been taken into consideration as of now in the literature. Exploring the thermodynamics and kinetics of the cell-system during the charge and discharge at different temperature with different methods, such as Galvanostatic Intermittent Titration Technique (GITT) and Electrochemical impedance spectroscopy (EIS) provides much-needed insights to elucidate the limits and obstacles to ion transport, which can then be addressed. EIS is one a key tool which provides the exchange current density, a measure of the rates of electron transfer as the ions migrate between the electrolyte and the electrodes, indicating the impedance of the different components in the cell at different frequencies. This is combined with Raman to further investigate these phase changes at different temperature.

The understanding gained of the limits and obstacles to charge transfer will be highly beneficial in designing better suited hard carbons to improve their overall cell performance in SIBs.
Enhancing Structural of P2-Type Layered Cathode Material for Sodium-Ion Batteries through Cu Substitution
Authors: Hyejin Kim , Myung Seung-Taek
Published: February 2024

Oxygen-redox-based layered cathode materials for Sodium-ion batteries (SIBs) have been recognized as a promising alternative to Lithium-ion batteries (LIBs) due to high energy density and additional capacity in the high voltage. However, their irreversible oxygen-redox activity during cycling leads to structural distortion and capacity fading. Herein, we introduce a layered P2-Na0.75[Li0.15Cu0.15Mn0.7]O2 cathode material, in which Cu substitution improves electro-conductivity and cyclability. Na0.75[Li0.15Cu0.15Mn0.7]O2 delivers a reversible capacity of 170 mAh g-1 at 0.1C in Na cell. Operando-XRD measurement display the material maintain the P2 structure even upon full Na+ extraction and insertion. Furthermore, magnetic susceptibility provide further information Cu2+/Cu3+, Mn3+/Mn4+, and O2-/(O2)n- ion distribution in Na0.75[Li0.15Cu0.15Mn0.7]O2. This research highlight the effect of Li and Cu doping in P2-type layered materials and the contribution of oxygen redox to additional capacity in high voltages, suggesting the potential for future development of cathode materials for Na-ion batteries with oxygen redox.
Enabling High-Capacity Electrochemical Magnesium Intercalation in Prussian Blue Cathode Via Synthesis Route Optimization
Authors: Setiawan Dedy , Hwang Jiwon , Choi Jin , Hong Seung-Tae
Published: February 2024

Magnesium-ion batteries (MIBs) have emerged as a promising candidate for post-lithium-ion batteries. However, their widespread adoption is hindered by the limited number of host materials that can intercalate magnesium ions reversibly in a nonaqueous electrolyte with a high operating voltage, such as Prussian Blue analogues. Unfortunately, the capacity of Prussian Blue is by far limited (<100 mAh g−1), resulting in low energy density, despite their high operating voltage. In this study, we present a systematic synthesis route optimization that allows for high-capacity magnesium ion insertion into Prussian Blue. Our defect-free and water-free Prussian Blue demonstrates reversible magnesium intercalation with a first discharge capacity of 127 mAh g−1 at 25 °C and 156 mAh g−1 at 60 °C, with an average discharge voltage of ~2.1 V (vs. Mg/Mg2+) in a nonaqueous, chloride-free electrolyte. The high-capacity magnesium ion insertion into our optimized Prussian Blue offers insights into the importance of material preparation for high-energy cathode materials in MIBs.
Designing Architected Nickel Hydroxide Cathodes for Rechargeable Alkaline Nickel–Zinc Batteries
Authors: Kimmel Samuel W. , DeBlock Ryan H. , Manley Jaret A. , Gibson Benjamin M. , Silguero Cory M. , Rolison Debra R. , Rhodes Christopher P.
Published: February 2024

Now that dendrite-suppressing Zn sponge anodes developed at the U.S. Naval Research Laboratory [1] offer a safer route to aqueous batteries that can power a wide range of end uses including electric vehicles, portable electronic devices, and backup energy storage, we need better cathodes. With high rate capability and deep theoretical utilization of the zinc (DOD ≥ 40%) now routine in alkaline electrolytes, storing and delivering more than one electron per metal-centered active material in the cathode is next. We focus on moving the Ni cathode past the 0.8–0.9 electrons per Ni characteristic of fabricating the cathode using β-Ni(OH)2 to tap the extra capacity inherent to α-Ni(OH)2 (theoretical: 1.67 electrons/Ni). Substituting Al3+ into α-Ni(OH)2 stabilizes the alpha phase from conversion to beta phase upon contact with and cycling in aqueous KOH and shifts positive the cell voltage for oxygen evolution (OER), the parasitic charging reaction that affects coulombic efficiency and limits cycle life [2]. We have now redesigned a classic powder composite Ni cathode (carbon black + Ni(OH)2 + binder) into an architected Ni electrode to improve charging efficacy. Using microwave-assisted deposition of Al-substituted α-Ni(OH)2 nanosheets onto a freestanding carbon nanofiber paper electrode wires the active material in 3D to the current-collecting carbon throughout the volume of the electrode. The architected Ni cathodes are tested in alkaline cells versus zinc sponge anodes and demonstrate that architected electron-wiring improves the capacity, rate, and cycle stability of Ni cathodes relative to conventional powder-composite electrodes. Varying the synthetic conditions achieves mass loadings that approach technologically relevant values. The enhanced electrochemical performance of architected Ni cathodes and architected Zn anodes provides a pathway to energy dense, safe, rechargeable Ni–Zn batteries.

[1] Parker, J.F.; Chervin, C.N.; Pala, I.R.; Machler, M.; Burz, M.F.; Long, J.W.; Rolison, D.R. Rechargeable Nickel–3D Zinc Batteries: An Energy-Dense, Safer Alternative to Lithium-Ion. Science
2017, 356, 415–418 (10.1126/science.aak9991).

[2] Kimmel, S.W.; Hopkins,B.J.; Chervin, C.N.; Skeele, N.L.; Ko, J.S.; DeBlock, R.H.; Long, J.W.; Parker, J.F.; Hudak, B.M.; Stroud, R.M.; Rolison, D.R.;Rhodes, C.P.Capacity and Phase Stability of Metal-Substituted α-Ni(OH)₂ Nanosheets in Aqueous Ni–Zn Batteries. Mater. Adv.
2021, 2, 3060–3074 (10.1039/D1MA00080B).
High-Performance Organic Electrode Materials
Authors: Wu Zhenzhen , Zhang Shanqing
Published: February 2024

Organic electrode materials (OEMs) are one of next-generation of electrode materials, allowing the wide range of application in metal ions batteries (MIBs) like lithium-ions batteries, sodium-ions batteries, zinc ions batteries, aluminium-ions batteries, and so on. OEMs are attractive because of their molecular adjustability, flexible nature, green resources, and low-environmental footprint. However, the nature of electronic insulation and solubility in organic electrolytes degrade the battery performance of OEMs. In order to address these challenges, we have concluded and applied useful strategies (i.e., molecular and morphological engineering) to achieve fast ionic/electronic conductivity and stability in the cycling process. Molecular engineering includes mitigating the number and kinds of redox-active centres to enhance the specific capacity, grafting electron-withdrawing/donating groups to adjust the working voltage, increasing the degree of polymerization to decrease the solubility, extending the conjugated structure to enhance the electronic conductivity, and so on. Morphological engineering is regarding to conceive 0D, 1D, 2D, and 3D OEMs for optimizing the ionic and electronic conducting pathway. In a word, through molecular and morphological engineering, OEMs could be promising electrode materials for high performance MIBs.

Figure caption: The chemical molecular structure, morphology, and the types of OEM-based batteries with the illustration of molecular and morphological engineering strategies.

Figure 1
Surface Engineering of Ni-Rich Cathode with Spinel Structure for Improved Performance of All-Solid-State Batteries
Authors: Jin Wooyoung
Published: February 2024

All-solid-state batteries are emerging as the most promising next-generation batteries due to their ability to achieve high energy density, along with their non-flammable properties. However, all-solid-state batteries face difficulties in commercialization, owing to high interfacial resistance and electrochemical instability at the interface. In particular, the compatibility and contact area issues of the interface between the solid electrolyte and cathode materials are still problematic. To address this issue, we applied a surface treatment in the form of a spinel structure to the Ni-rich cathode material. This surface modification not only improved cycle life by increasing the surface stability of the cathode material but also reduced the internal resistance by creating an ionic conductivity network that facilitated the transport of Li-ions through the cathode. Our results suggest that surface engineering of the Ni-rich cathode has the potential to develop long cycle life and high performance in all-solid-state batteries.
Solid-State Polymer Battery: Manufacturing Process and Characterization
Authors: Touidjine Amina , Calmes Vincent , Dendary Mélanie , Borel Philippe , Truche Paulin , Dussart Thibaut
Published: February 2024

Solid-state batteries are a promising technology that could provide higher energy density, better safety, longer cycle life and a wider operating temperature range than current commercial LiBs
[1]
.

The solid electrolyte is the main component of all-solid-state batteries. It can be ceramic, glass, polymer, or a mixture. Solid Polymer Electrolyte (SPEs) have received distinctive attention, especially by industry, owing to their potential advantages such as safety, lightweight, high flexibility, and realistic processability. However, despite fast growing interest in solid-state technology, reports on the scalable production of all-solid-state lithium-ion batteries using electrodes with meaningful areal capacities are rather scarce
[2]
. Moreover, chemical, and mechanical challenges remain. The intimate contact between the electrode and the solid electrolyte is difficult due its non-infiltrative nature. This lack of intimate contact severely limits the cycling properties
[3]
. The development of effective strategies to alleviate the issue of physical contact is imperative in the engineering of solid-state batteries
[4]
.

In the frame of SAFELiMOVE (Advanced all Solid stAte saFE
Lithium Metal technology tOwards Vehicle Electrification) project, we assemble a solid-state pouch based on lithium metal anode, a solid polymer electrolyte layer and a compatible cathode. In work, we report on a reliable fabrication process of large-scale all-solid-state lithium-ion batteries using cathodes prepared by CIDETEC, lithium anode provided by Hydro-Quebec, polymers provided by CICe, inorganic filler provided by SCHOTT and a solid polymer electrolyte manufactured at SAFT.

All-solid-state lithium-ion battery pouch cells have been successfully built with consistent electrochemical performance. Cycling that shows the good performance of those cells and the lesson learned regarding their cycling conditions will be presented.

[1] J. Motalli, “A solid future Nature, 526, S96 (2015)

[2] Ningxin Zhang et al “Scalable preparation of practical 1Ah all-solid-state lithium-ion batteries cells and their abuse tests”, Journal of Energy Storage 59 (2023) 106547

[3] Li et al.“Atomically Intimate Contact between Solid Electrolytes and Electrodes for Li Batteries” Mater 1, 1001-1016, October 2, 2019.

[4] Theodosios Famprikis, Pieremanuele Canepa, James A. Dawson, M. Saiful Islam and Christian Masquelier“Fundamentals of inorganic solid-state electrolytes for batteries” Nature Materials-August 2019.

Figure 1
Transition Metal Doped BiVO4 Photoanodes: A Mechanistic Study
Authors: García-Tecedor Miguel , García-Eguizábal Alejandro , Barawi Moran Mariam , Gomez‐Mendoza Miguel , Energy Imdea , Villar-Garcia Ignacio J , Liras Marta , de la Peña O'Shea Victor A.
Published: February 2024

BiVO4 has emerged as one of the most promising materials to fabricate efficient photoanodes for photoelectrochemical (PEC) solar water splitting. BiVO4 is an n-type semiconductor, with a 2.4 eV bandgap and a theoretical solar to hydrogen (STH) efficiency of 9.2% with a maximum photocurrent of 7.5 mA cm2 under AM 1.5 G illumination, low overpotential and favourable band-edge positions towards the Oxygen Evolution Reaction (OER).1 However, BiVO4 also presents poor electron transport, high surface recombination and slow water oxidation kinetics. Hence, enormous efforts have been made in the past few years to mitigate these drawbacks through different approaches such as nanostructuring,2 doping,3 heterostructuring,4 and the use of efficient co-catalysts.5

The present study proposes a transition metal doping (Ni, Fe and Co) of BiVO4 photoelectrodes that boosts their water oxidation performance. The origin of this enhanced performance towards Oxygen Evolution Reaction (OER) was studied by a combination of a suite of structural, chemical, and mechanistic advanced characterization techniques including X-Ray Photocurrent Spectroscopy, Electrochemical Impedance Spectroscopy and Transient Absorption Spectroscopy, among others.

[1] J. Li and N. Wu, Catal. Sci. Technol., 2015, 5, 1360–1384.

[2] S. P. Berglund, D. W. Flaherty, N. T. Hahn, A. J. Bard and C. B. Mullins, J. Phys. Chem. C, 2011, 115, 3794–3802.

[3] S. K. Pilli, T. E. Furtak, L. D. Brown, T. G. Deutsch, J. A. Turner and A. M. Herring, Energy Environ. Sci., 2011, 4, 5028–5034.

[4] J. Su, L. Guo, N. Bao and C. A. Grimes, Nano Lett., 2011, 11, 1928–1933.

[5] D. K. Lee and K.-S. Choi, Nat. Energy, 2018, 3, 53–60.
High Entropy Induced γ-NiOOH Formation in Layered Double Hydroxide as Highly-Active and Ultra-Stable Electrocatalyst for Oxygen Evolution Reaction
Authors: Nguyen Thi Xuyen , Tsai Chia-Chien , Nguyen Van Thanh , Huang Yan-Jia , Su Yen-Hsun , Xie Rui-Kun , Lin Yu-Jung , Lee Jyh-Fu , Ting Jyh-Ming
Published: February 2024

Developing a low-cost and highly efficient oxygen evolution reaction (OER) electrocatalyst and understanding the underlying reaction mechanism are critical for sustainable renewable energy conversion and storage. In this study, high entropy layered double hydroxide (LDH) was self-supported on nickel foam using a simple hydrothermal method. The resulting binder-free high entropy LDH consisting of five different transition metals of Fe, Ni, Co, Mn, and Cr exhibits an excellent OER activity in alkaline condition with a low overpotential of 218 mV at a current density of 50 mA cm-2. It is superior to the binary, ternary, and quaternary-metal LDH counterparts. We demonstrate that the high entropy LDH possesses ultra-stable electrochemical stability at a high current density of 400 mA cm-2 for 600 h. The modulation of electronic structure facilitates the formation of the highly active γ-NiOOH and the shifting of the d-band center, resulting the outstanding OER performance. The excellent catalytic activity and stability of the high entropy LHD make it is as a highly potential candidate for commercial use.
Stabilization of Silicon Photoanode By Hafnium Zirconium Oxide Interlayer for Efficient Solar Water Oxidation
Authors: Lee Sola , Choi Sungkyun , Atwater Harry A. , Jang Ho Won
Published: February 2024

Photoelectrochemical devices, which convert solar energy into sustainable hydrogen, are promising for carbon neutralization. The prerequisites for the photoelectrode materials are absorbing a wide range of the solar spectrum, cost-effectiveness, long carrier lifetime, and so on. Silicon, which has a bandgap of 1.12 eV, has been of prime interest because of its excellent charge carrier mobility, earth abundance, and high crystallinity. However, instability in the electrolytes, poor catalytic activity, and negative valence band position hampers its application. The design of metal-insulator-semiconductor (MIS) structures is a promising strategy for boosting catalytic surface reactions with high stability. Herein, we report the interface engineering of MIS photoanodes with enhanced stability for water oxidation. First, we investigate the effect of poling direction of hafnium zirconium oxide (HZO) with a few-nm thickness as a surface passivation layer. Then, additional Ni/NiFe layered double hydroxide (LDH) catalysts are introduced to accelerate surface catalytic reactions. Harmonizing the HZO interlayer and Ni/NiFe LDH on silicon performs with a high current density of 26.6 mA cm-2 at 1.23 V vs. reversible hydrogen electrode with stability. This study demonstrates the rational design of MIS structure and manipulating hierarchical photoanodes' interface to boost stability and charge carrier kinetics.
(Invited) Highly Nanoporous Hematite with Optimal Doping for an Efficient Photoelectrochemical Water Splitting
Authors: Jang Ji-Hyun
Published: February 2024

In this study, we propose a highly nanoporous hematite structure having under 5 nm hole diffusion pathways via an optimized doping method based on Density Functional Theory (DFT) calculations. The superiority of highly nanoporous structure with the synergistic effects of a facilitated Kirkendall effect and optimal doping condition were clearly proved by the experimental analyses. The optimized prous photoanode prepared with an optimal doping conditoin (Ge:Ti:Sn doped hematite) and the subsequent dopositon of an oxygen evolution reaction co-catalyst NiFe(OH)x showed a maximum photocurrent density of 5.1 mA cm-2 at 1.23 VRHE, which is 3.3-fold higher than that of reference Ti:Sn hematite due to enhanced surface reaction kinetics. This study provides a significant breakthrough in dramatically improving the low PEC performance of hematite-based photoanodes with an short-hole diffusion pathway issue through optimal co-doping and nanostructuring.
(Invited) Modulation of Photocatalytic Activity with Oxygen Vacancies in Metal Oxides
Authors: Wu Nianqiang
Published: February 2024

Oxygen vacancies commonly exist in metal oxides. The presence of oxygen vacancies alters electronic band structure, changes the chemical valences of metal ions, createS surface disorder and etc. This talk will discuss how oxygen vacancies will modulate light absorption, charge separation, migration, recombination and injection to electrolytes, which in turn affects photocatalytic activities of metal oxides.
Photoelectrochemical Nitrate Reduction to Ammonia Using Metal Oxide Based Photosensitisers
Authors: Mistry Elan D.R. , Rettie Alex J.E.
Published: February 2024

Ammonia is one of the most important chemicals synthesised presently. It supports the lives of billions around the world through its utilisation as a precursor for fertilisers, enhancing agricultural yield. It has also been proposed that ammonia could be employed as a carbon free hydrogen storage molecule due to its high hydrogen content (40% higher than methanol).

Currently, ammonia primarily is synthesised through the energy-intensive Haber Bosch process. This entails combining dinitrogen and hydrogen under high temperatures (300-500 °C) and high pressures (150-200 atm). These strenuous conditions are due to the extreme difficulty in cleaving the dinitrogen triple bond. This process, in addition to using steam reforming to produce hydrogen, results in large carbon dioxide output.

Therefore, it is necessary to devise alternative methods to synthesise green ammonia. Photoelectrochemical synthesis of ammonia is one such route that couples electrochemical and photochemical processes to reduce the overpotential needed. Additionally, from the economic and environmental perspective, nitrate reduction to produce ammonia is a better option. Nitrates are present in the environment naturally or contaminated from run off fertilisers. These present a threat that if consumed in large quantities can lead to cancers and if left to accumulate in waters, lead to environmental issues such as eutrophication.

This work thus focuses on the synthesis of materials to reduce nitrates to ammonia photoelectrochemically. P-type semiconductors with a conduction band position that encompass the reduction potential of nitrate to ammonia are employed. Utilising different p-type metal oxide photosensitisers such as copper oxide, nickel oxide and cobalt oxide, the surfaces are modified with metal catalysts to improve the conversion efficiency of nitrate to ammonia. The concentration of nitrite (the first reductive product) and ammonia formed is evaluated using ion chromatography. Additionally, the concentration of hydrogen and nitrogen formed will be evaluated using gas chromatography. To further evaluate the efficacy of these materials, the faradaic efficiency and yield rates for nitrate reduction are evaluated. The quality of the materials chosen are be judged on their selectivity for adsorption and reduction, and their stability.
Light-Induced Ammonia Generation over Defective Carbon Nitride Modified with Pyrite
Authors: Zander Judith , Marschall Roland
Published: February 2024

The challenge to mitigate climate change and to limit global warming to well below 2 °C according to the Paris Agreement, requires a reduction of greenhouse gas emissions not only in transportation, but also in industry.[1] The Haber-Bosch process for the production of ammonia, NH3, is one of the most important industrial processes, but significantly contributes to the world’s annual CO2 emissions.[2] Photocatalytic reduction of dinitrogen (NRR) offers a sustainable alternative for the synthesis of ammonia. Some of the highest activities so far were achieved with carbon nitride (C3N4) photocatalysts, especially after the introduction of nitrogen vacancies.[3] Carbon nitrides are earth abundant, non-toxic, low-cost polymeric materials, with a suitable band gap for visible light absorption. To overcome the inherently fast charge carrier recombination that diminishes the efficiency, heterojunctions with a second photocatalyst are widely investigated.[4] Another common approach in the design of photocatalyst for the NRR is nature-inspired. Herein, mainly sulphur, iron and molybdenum containing materials are investigated, inspired by the composition of the active centre in nitrogenase enzymes.[5]

In this contribution we present composite materials of FeS2 and vacancy-rich VN-C3N4, thereby combining both strategies of heterojunction formation and bio-inspiration, as well as that of defect engineering in C3N4, to increase the number of active sites.[6] The composites yield significantly higher amounts of ammonia after light irradiation for 7 h, compared to both FeS2 and VN-C3N4 alone. Hydrogen is produced as the only by-product. A combination of control experiments and material characterisation before and after light irradiation revealed that iron in FeS2 coordinates to VN-C3N4 at the defect site. Cyano-groups at these sites are activated via π-back-donation and subsequently converted into ammonia. Thus we could prove that – at least initially – ammonia is generated not from the N2 gas, but from the C3N4-framework itself.

References:

[1] UNFCCC, Adoption of the Paris Agreement, 21st Conference of the Parties, Paris, 2015.

[2] J. G. Chen, R. M. Crooks, L. C. Seefeldt, K. L. Bren, R. M. Bullock, M. Y Darensbourg, P. L. Holland, B. Hoffman, M. J. Janik, A. K. Jones, M. G. Kanatzidis, P. King, K. M. Lancaster, S. V. Lymar, P. Pfromm, W. F. Schneider, R. R. Schrock, Science
2018, 360, 6391.

[3] a) W. Wang, H. Zhang, S. Zhang, Y. Liu, G. Wang, C. Sun, H. Zhao, Angew. Chem. Int. Ed.
2019, 58, 16644, b) X. Li, X. Sun, L. Zhang, S. Sun, W. Wang, J. Mater. Chem. A
2018, 6, 3005.

[4] J. Fu, J. Yu, C. Jiang, B. Cheng, Adv.
Energy Mater.
2018, 8, 1701503.

[5] K. Tanifuji, Y. Ohki, Chem.
Rev.
2020, 120, 5194.

[6] J. Zander, J. Timm, M. Weiss, R. Marschall, Adv.
Energy Mater. 2022, 12, 2202403.

Figure 1
Artificial Photosynthesis of Ammonia by Semiconducting Plasmonic NIR Energy
Authors: Zhao Zhenhuan
Published: February 2024

Artificial photosynthesis of ammonia is one of the most promising paths toward carbon neutrality and sustainability. However, nitrogen photo-fixation to produce ammonia in ultrapure water is still challenging due to the thermodynamic and kinetic requirements of the nitrogen reduction reaction. An ideal photocatalyst is expected to have energetic electrons to drive the nitrogen reduction reaction, as well as enough affinity for chemisorption and activation of nitrogen molecules at the surface. Compared with plasmonic metal catalysts, plasmonic semiconducting nanomaterials are excellent candidates due to the tunable plasmon absorption over a wide range of spectra allowing efficient utilization of solar energy, abundant hot carriers that may overcome the interfacial energy barriers, and low-cost. The localized surface plasmonic resonance (LSPR) effects can also promote charge separation and interfacial transfer. Here, we report metal oxides with tunable oxygen concentration and copper chalcogenides with tunable copper deficiency for photocatalytic nitrogen reduction in ultrapure water. Efficient ammonia production has been achieved under near-infrared (NIR) light illumination. We have demonstrated that for plasmonic semiconducting photocatalysts, the performance is not only dictated by the defects, their negative effects in trapping carriers are also important.

Figure 1
Rh-WO3 Electrocatalyst for Hydrogen Evolution Reaction in the Alkaline Seawater Electrolyte
Authors: Nguyen Ngoc Anh , Chuluunbat Enkhjin , Choi Ho Suk
Published: February 2024

One potential strategy to develop hydrogen evolution electrocatalysts for producing sustainable hydrogen in water electrolysis is creating electrocatalysts with low-cost, high activity, and high stability. Herein, we show that low-loading metal-based tungsten oxide (WO3) can be used as electrocatalysts for the hydrogen evolution reaction (HER) in acid, alkaline, and alkaline seawater electrolytes. Among prepared electrocatalysts, rhodium (Rh)-WO3 exhibits a high HER activity with the values of overpotential of 48, 116, and 98 mV to obtain a current density of 10 mA.cm-2 in acid, alkaline, and alkaline seawater electrolytes, respectively. In addition, the Rh-WO3 electrocatalyst shows high stability during the HER operation for over 60,000s. Besides, the application of Rh-WO3 electrocatalyst as cathode and commercial ruthenium oxide (RuO2) as an anode for overall water splitting show excellent efficiency with only a potential of 1.45 V to a current density of 10 mA.cm-2 in the alkaline-seawater electrolyte. The Rh-WO3//RuO2 cell also exhibits high stability for over 40,000s. The results provide evidence that Rh-WO3 can be a promising HER catalyst for sustainable hydrogen production via alkaline-seawater electrolysis application, as show in Figure 1.

Figure 1
Single Crystal (K,Na)Nb)3/CuO Heterostructures for Synergistic Photo-Piezocatalytic Activity
Authors: Im Eunmi , Min Yuho , Moon Geon Dae
Published: February 2024

In this study, we designed a heterostructure piezo-photocatalyst composed of Ba, Li doped- (K,Na)NbO3 (KNN) single-crystal microcuboids and CuO nanodots. KNN was selected because of its high piezoelectric coefficient (d33
), good chemical stability, and environmental friendliness. As a cocatalyst, CuO was considered owing to its advantages such as narrow bandgap, low cost, and nontoxicity. The n-type semiconducting Pb-free KNN single-crystal ferroelectric microcuboids (~30 μm) were synthesized by molten-salt reaction. Then, p-type semiconducting CuO nanodots (less than 5 nm) were uniformly decorated onto KNN microcuboids via deposition of Cu(OH)2, followed by conversion to CuO through calcination. From our heterostructure, it is expected that excellent piezoelectric properties could be obtained from KNN single-crystal microcuboids and a high surface area for catalytic reactions is guaranteed by CuO nanodots that are evenly deposited on the surface of KNN without aggregation. The novel KNN/CuO micro/nano heterostructures exhibited increased current density, and enhanced removal organic dye (RhB) efficiencies under the ultrasonic vibration when compared with bare KNN single-crystal catalysts. Specifically, the reaction rate constant (k) for the photo-piezocatalytic RhB dye degradation of the KNN/CuO micro/nano heterostructure exhibited ~ 0.093 min-1, which is higher when compared with other KNN-based piezo, photo, and photo-piezocatalysts. Additionally, the coupled photo-piezocatalyst for KNN/CuO realized an enhanced RhB dye degradation efficiency of 1.6 times and 48.6 times higher when compared with individual piezocatalytic and photocatalytic dye degradation capabilities, respectively. Our approach could provide insights into the design of heterostructure photo-piezocatalysts containing single-crystal ferroelectrics, which requires the enhancement of the photo-piezocatalytic activities.