bluuebunny/crossref_metadata_2025 huggingface dataset:
High-Performance CO2 and H2O Co-Electrolysis Based on Micro-Structured Hollow Fiber Solid Oxide Electrolysis Cell
Authors: Yan Peng , Li Kang
Published: February 2024

The world is dedicated to achieving Carbon Neutrality and Circular Economy in the next decades by circulating carbon element. This makes the research related to energy and environment more stringent and urgent. Solid oxide electrolysis cell (SOEC) has been regarded as the key enabling technologies to mitigate the issues and meanwhile can take full use of the intermittent renewable electricity. Herein, we designed a multi-channel hollow fiber SOEC, which presents sub-millimeter channels and separate domains of mechanical strength and catalytic reactions, to split CO2 (and H2O) to CO (and H2), which can be used as the feedstock for Fischer-Tropsch and methanol synthesis. The results show high current density, good performance durability, and low concentration polarization, and thus the new design can achieve compact design together with excellent performance with volumetric productivity of above 125 kmol/m3/hr at 750 degC. Co-electrolysis performance is further explored by incorporating newly designed catalyst for further enhancement.

Figure 1
(Invited) Dry Process for Thick Electrode in Batteries
Authors: Meng Shirley
Published: February 2024

Due to its high operating voltage and cobalt-free chemistry, the spinel-type LiNi0.5Mn1.5O4 (LNMO) cathode material has attracted great interest as one of the few next-generation candidates capable of addressing this combination of challenges. However, severe capacity degradation and poor interphase stability have thus far impeded the practical application of LNMO. In this study, by leveraging a dry electrode coating process, we demonstrate LNMO electrodes with stable full cell operation and ultra-high loading. This excellent cycling stability is ascribed to a stable cathode-electrolyte interphase for charge transfer and ion transport, a highly distributed and interconnected electronic percolation network, and robust mechanical properties. High-quality images collected using plasma focused ion beam scanning electron microscopy (PFIB-SEM) provide additional insight into this behavior, with a complementary 2-D model illustrating how the electronic percolation network in the dry-coated electrodes more efficiently supports homogeneous electrochemical reaction pathways. These results strongly motivate that LNMO as a high voltage cobalt-free cathode chemistry combined with an energy-efficient dry electrode coating process opens the possibility for sustainable electrode manufacturing of cost-effective and high-energy-density cathode materials.
Facile Preparation of Porous Ni-YSZ Electrode Composite Material: From Highly Dense to Desirable Electrode Porosity Even without Pore Former
Authors: Macalisang Christine Mae , Imperial James Francis , Cervera Rinlee Butch
Published: February 2024

Ni-YSZ is a key electrode material for solid oxide electrochemical cells (SOC) applications, such as fuel or electrolysis cell applications. The number of active sites, specifically the triple-phase boundaries (TPB), strongly affects the electrode performance. Thus, in order to achieve good electrode performance, a desirable microstructure of the electrode is essential. This study investigated the effect of precursor particle size without using pore former in developing porous Ni-YSZ electrode materials. Precursors were prepared with different particle sizes using a planetary ball mill. In comparison, Ni-YSZ with carbon black as a pore former was also prepared. From the XRD patterns, major peaks can be attributed to the cubic phases of NiO and YSZ. SEM images revealed that a highly dense as-sintered NiO-YSZ electrode was achieved; however, a desirable porous microstructure was obtained after reduction to Ni-YSZ, even without a pore former. In comparison, the prepared electrode with carbon black pore former has a larger pore size than the sample prepared without pore former. The obtained total bulk conductivities for the reduced Ni-YSZ without pore former at 700 oC is 3.94x10-1 S/cm with Ea of 0.02 eV at 500-700 oC. Thus, a desirable porous Ni-YSZ electrode with more TPBs and high total conductivity can be achieved even without a pore former.

Figure 1
Void Growth Dynamics in Solid-State Batteries
Authors: Vishnugopi Bairav Sabarish , Naik Kaustubh Girish , Mukherjee Partha P.
Published: February 2024

Solid-state batteries (SSBs) can potentially offer improved energy density and safety, when compared to current lithium-ion batteries. Despite their irrefutable theoretical promise, further advancement of SSBs relies on developing a comprehensive understanding of various fundamental aspects including electro-chemo-mechanics, transport interactions, morphological evolution and related failure modes at solid-solid interfaces. Amongst the wide range of challenges, the formation and evolution of interfacial voids at the lithium-metal/solid-electrolyte interface during stripping is critical, due to its associated effect on internal short-circuit and cell failure during subsequent plating. The void growth phenomenon in SSBs is jointly determined by different factors such as the self-diffusion kinetics and mechanical response of lithium, reaction distribution at the solid-solid interface, and operating conditions such as external pressure and temperature. In this presentation, the pivotal role of reaction heterogeneity on the contact evolution process, along with key descriptors such as the lithium microstructure, surface morphology and contact percolation are discussed. The underlying asymmetry in terms of the competing electrochemical/mechanical processes and contact evolution during plating and stripping is highlighted. Lastly, the influence of non-uniformities in external pressure and temperature on the occurrence of disparate void growth patterns and electrochemical response is examined in this presentation.
(Invited) Achieving Extreme High Ion-Current Densities in Tailored Materials, Structures, and Interfaces
Authors: Wachsman Eric
Published: February 2024

Rate capability is a limiting factor in solid oxide fuel cells (SOFCs), solid oxide electrolysis cells (SOECs), and oxide-based solid-state lithium (SSLiBs) and sodium (SSNaBs) batteries. In this presentation we will explain the roles of composition, structure, and interfaces in achieving extremely high current densities, and demonstrate SOFC/SOEC current densities of 5 mA/cm2 at 650°C, and SSNaB and SSLiB current densities of 30 mA/cm2 and 100 mA/cm2, respectively, at room temperature.
Mechanics-Coupled Interface Kinetics in Solid-State Batteries
Authors: Chatterjee Debanjali , Naik Kaustubh Girish , Vishnugopi Bairav Sabarish , Mukherjee Partha P.
Published: February 2024

Solid-state batteries (SSBs) utilizing lithium metal anode are promising candidates for next-generation energy storage systems, offering high energy density and enhanced safety. However, imperfect electrochemical contact at the lithium-solid electrolyte (SE) interface results in transport limitations and high interfacial resistance, posing a critical bottleneck on rate performance. Solid-solid point contacts at the interface lead to stress hotspots and current-focusing, resulting in localized lithium deposition, filament growth and mechanical fracture of the SE. The application of external pressures potentially enables enhanced electrochemical contact at such solid-solid interfaces. Under these circumstances, non-uniform stresses arising due to the heterogeneous nature of interface morphology and surface defects play a critical role in the onset of interface instability. In this work, we present a mechanistic description of stress-coupled reaction kinetics governing the evolution of solid-solid interfaces in SSBs. We demonstrate how the energetic contribution of interfacial stresses alters the open circuit potential and exchange current density, which further affects the Butler-Vomer kinetics and morphological stability of the lithium-SE interface. Through our analysis, we illustrate the strong dependence of mechanical stress contributions to reaction current on the material characteristics of the electrode-SE pair and delineate interface stability regimes for different formulations of mechanics-coupled reaction kinetics interactions.
Highly Concentration Aqueous Electrolytes for Zinc Metal Batteries
Authors: Al Kathemi Ibrahim , Antonietti Markus , Bouchal Roza
Published: February 2024

Aqueous zinc batteries (AZB) emerged as a promising technology for renewable and low-cost storage devices.[1] Zinc (Zn) metal features high abundance, intrinsic safety, low cost (~USD $2 kg-1) and high theoretical capacity (820 mA h g-1).[2,3] However, AZBs do suffer from low Coulombic efficiency, dendrite growth and parasitic hydrogen evolution reaction (HER), which restrict their practical applications.[4] To combat this problem, highly concentrated electrolytes (HCEs) are employed to improve the cycling stability of AZBs.[5]

In this work, we demonstrate that aqueous HCEs based on Zn and organic salts are a very effective way to address these issues. Aqueous eutectic electrolytes were obtained by simply optimizing the salt ratio, as evidenced by the low liquid-to-solid transition temperature. These unique HCEs feature a wider electrochemical stability window and an improved ionic conductivity. Additionally, the high-density of Zn cations near the electrode surface results in reversible and stable Zn electrodeposition - with relatively low overpotentials in comparison to other reported hybrid Zn electrolytes. Thus, this work presents an efficient, economically attractive and simple approach for the development of HCEs for practical applications of AZBs.

References

[1] J. Yang, B. Yin, Y. Sun, H. Pan, W. Sun, B. Jia, S. Zhang, T. Ma, Nano-Micro Lett.
2022, 14, 1–47.

[2] Y. Shi, Y. Chen, L. Shi, K. Wang, B. Wang, L. Li, Y. Ma, Y. Li, Z. Sun, W. Ali, S. Ding, Small
2020, 16.

[3] D. Kundu, B. D. Adams, V. Duffort, S. H. Vajargah, L. F. Nazar, Nat. Energy
2016, 1, 1–8.

[4] H. Qin, W. Kuang, D. Huang, X. Zhang, J. Liu, L. Yi, F. Shen, Z. Wei, Y. Huang, J. Xu, H. He, J. Mater. Chem. A
2022, 10, 17440–17451.

[5] F. Wang, O. Borodin, T. Gao, X. Fan, W. Sun, F. Han, A. Faraone, J. A. Dura, K. Xu, C. Wang, Nat.
Mater.
2018, 17, 543–549.
Artificial SEI Layer Combined with Single-Ion Polymer Electrolytes to Prevent Dendrite Growth in Lithium Metal Batteries
Authors: Wan Jiajia , Liu Xu , Passerini Stefano , Paillard Elie
Published: February 2024

Li-metal batteries have the potential to become the next generation of batteries since they can provide an increased energy density vs. Li-ion batteries. However, the safety issue caused by the inhomogeneous Li deposition and Li dendrite growth greatly limits their commercial application. Several methods have been proposed to address this issue. On the one hand, when Li ions are released from one electrode and consumed at the other electrode, it causes a salt concentration gradient. Besides, the electrical migration of anions in the opposite direction aggravates the concentration of gradient since anions do not react at the electrodes. Fast dendritic growth then occurs when the current is high enough to fully deplete the Li+ ion at the anode during charge. Thus, suppressing concentration gradient by immobilizing the anions would in principle solve the fast dendritic growth issue. On the other hand, the Solid Electrolyte Interphase (SEI) plays a crucial role in the operation of Li metal batteries since it prevents further reduction and continuous electrolyte reaction. SEI derives from the passivation layer formed onto the surface of Li metal under dry air during lithium foil extrusion and then evolves further in contact with the electrolytes and during subsequent electrochemical Li stripping/plating. The SEI is inhomogeneous and since it contains lower resistance pathways for Li+ transport, it favors inhomogeneous deposition at any current. Thus, SEI engineering, in order to favor the homogeneity of current density and enhanced mechanical properties to confine lithium could, in principle, improve the performance of Li metal batteries.

Thus, we studied the use of single-ion conducting polymers with high cationic transference numbers (tLi+ close to 1) as artificial SEIs (art-SEIs) since they include immobile anions and thus prevent Li+ depletion during charge and, at the same time, improve lithium metal confinement and the homogeneity of current density. Our results show much improved homogeneity of Li deposition and cycling stability after single-ion art-SEI coating using an ether-based liquid electrolyte combined with a separator. Nevertheless, it could not enable long-term cycling as the separator does not enable homogeneous pressure and current density onto the lithium anode. Thus, the use of a single-ion conducting solid polymer electrolyte was combined with a single-ion conducting art-SEI (as illustrated in Figure 1). This strategy allows the suppression of salt concentration gradients, inhomogeneous pressure and current density, thus enables homogeneous Li deposition and long-term cycling of Li metal anode.

Figure 1
High-Performance Lithium Metal Batteries
Authors: Thangadurai Venkataraman
Published: February 2024

The success of rechargeable lithium-ion batteries (LIBs) has brought evident convenience to human society, but state-of-the-art LIBs with a graphite anode are approaching their energy density limits. Li metal is considered the ultimate anode material due to its ultra-high theoretical specific capacity of 3860 mAh g-1, which is more than 10 times higher than lithiated graphite. Nonetheless, Li metal anode suffers from poor safety and low cycling efficiency due to its high reactivity. Electrolytes that work with Li anode should possess excellent stability against Li metal or form a highly passivating interface. It is also critical to control the amount of Li in the cell, preferably having no excess Li at the anode side. In this talk next-generation solid state and hybrid electrolytes based on Li-stuffed garnets that enable high-performance Li metal batteries will be discussed.
Pinpointing the Blip: Coupled Transient Chemo-Mechanical Properties in Lithium-Metal Batteries
Authors: Thorsteinsson Gunnar , Chang Wesley , Wang Andrew , Herman Zoe , Katzman Libby , Steingart Daniel A.
Published: February 2024

Lithium-metal batteries experience significant mechanical stress as lithium is plated and stripped from the copper current collector during charge and discharge, respectively. Minimizing the negative effects of this stress on cell’s capacity retention over its cycle life is paramount to propel the high-density chemistry to the mainstream. To address this, acoustics have recently emerged as a viable experimental tool to monitor chemo-mechanical properties*.* In this work, we probe the underlying effects of coupled transient phenomena previously reported for Lithium-ion cells. By complimenting physical parameters—Young’s Modulus and damping coefficient, extracted from operando acoustics and pressure measurements—with simulations, we demonstrate that transient chemo-mechanical properties are in part resultant of ionic gradients in the electrolyte. These findings are in agreement with and build upon previous work on the acoustic signals of electrolytes by Wang et al, where acoustics were leveraged to extract mechanical parameters in situ,
and of Lithium-ion cells by Hodson et al, where nonlinearities in full-cell Lithium-ion acoustic signals were were hypothesized to be a result of electrolytes. Our results highlight the viability of acoustics as a valuable tool in battery research to non-invasively inspect transient phenomena in batteries.
Revealing the Cycling and Degradation Mechanism of Bi-Metallates As Anode Materials for Na-Ion Batteries
Authors: Brennhagen Anders , Skautvedt Casper , Cavallo Carmen , Skurtveit Amalie , Wragg David Stephen , Koposov Alexey , Sjåstad Anja Olafsen , Vajeeston Ponniah , Fjellvåg Helmer
Published: February 2024

Na-ion batteries (NIBs) represent an emerging alternative to modern Li-ion batteries. To improve the overall performance of NIBs it is crucial to develop new types of anode materials with high capacity and long cycle life. Among the anode candidates, materials operating under combined conversion and alloying mechanisms (CAMs) are considered as promising. They are capable of delivering high capacity, however, despite theoretical predictions the cycling stability is still below expectations. Therefore, a comprehensive understanding of the cycling and degradation mechanisms of CAMs is crucial to improve their performance. However, these materials undergo multiple chemical transformations, which often involves formation of amorphous and nanocrystalline phases during cycling. Such chemical complexity substantially impedes their full characterization and understanding.

Bismuth metallates, with a general formula of Bi-TM-O (TM = transition metal), is a group of ternary CAMs. Their general cycling mechanism consists of an irreversible conversion reaction, which leads to formation of Bi nanoparticles embedded in a Na-TM-O matrix during the first sodiation. This is followed by a reversible two-step alloying reaction leading to formation of Na3Bi with NaBi as an intermediate phase. In this work, we have used operando X-ray diffraction over the course of ∼30 cycles to study the cycling and degradation mechanisms of two CAMs - Bi2MoO6 and BiFeO3. With the help of ex situ X-ray absorption spectroscopy and pair distribution function (PDF) analysis, we have revealed new insights into these materials in addition to confirming the general cycling mechanism.

Both materials form the cubic phase of Na3Bi (c-Na3Bi) in the sodiated state with some noticeable differences. While, the hexagonal Na3Bi (h-Na3Bi) phase starts to form after 10 cycles in Bi2MoO6, a combination of c-Na3Bi and h-Na3Bi can be observed after the first cycle in BiFeO3. The formation of c-Na3Bi is kinetically favorable in these systems, while h-Na3Bi is the more thermodynamically stable and, therefore, forms later in the cycling process. Both materials shows three distinct regions of capacity degradation, where the first is initiated by a growth in the crystallite sizes of Bi-particles. This is followed by a disappearance of the Bi-phase as the second step. The last degradation phase is related to the disappearance of the NaBi-phase and locking the system in the sodiated state. The present talk will discuss the mechanisms of these degradation steps in view of the future development of CAMs in greater details.

Figure 1
An Ultrafast, Durable, and High-Loading Polymer Anode for Aqueous Zinc-Ion Batteries and Supercapacitors
Authors: Wang Xiaolei
Published: February 2024

With high theoretical capacities (820 mAh g−1 and 5855 mAh cm−3), suitable electrochemical potential (−0.763 V vs standard hydrogen electrode), low cost, and rich abundance of component materials, aqueous zinc-ion batteries (ZIBs) and capacitors (ZICs) have exhibited great promise for grid-level energy storage and other stationary applications. Zn metal as excessive Zn are often used to compensate for the uncontrollable dendritic growth, corrosion behaviour, and low Coulombic efficiency (CE) of the Zn metal. As such, most of the ZIBs and ZICs developed using these electrode materials exhibited actual device energy and power densities that were significantly lower than the corresponding theoretical values. Another key performance metric that needs to be improved in ZIBs is their high-rate charge and discharge. In addition to the dendrite-derived problems commonly experienced in batteries based on other metal anodes, ZIBs are disadvantaged by hydrogen gas evolution from water decomposition especially under high-rate charge/discharge, leading to poor cycle life.

Herein, an ultrafast, stable, and high-loading polymer anode for aqueous Zn-ion batteries and capacitors (ZIBs and ZICs) is developed by engineering both the electrode and electrolyte. The anode polymer is rationally prepared to have a suitable electronic structure and a large π-conjugated structure, whereas the electrolyte is manufactured based on the superiority of trif late anions over sulfate anions, as analyzed and confirmed via experiments and simulations. This dual engineering results in an optimal polymer anode with a low discharge potential, near-theoretical capacity, ultrahigh-loading capability (≈50 mg cm−2), ultrafast rate (100 A g−1), and ultralong lifespan (one million cycles). Its mechanism involves reversible Zn2+/proton co-storage at the carbonyl site. When the polymer anode is coupled with cathodes for both ZIB and ZIC applications, the devices demonstrate ultrahigh power densities and ultralong lifespans, far surpassing those of corresponding Zn-metal-based devices.

Figure 1
Insights into Perylene-Tetra-Carboxylate Derivatives as Versatile Anode Materials for Alkali-Metal-Ion Batteries
Authors: Lenzer Anja , Asenbauer Jakob , Shi Kai , Eisenmann Tobias , Bresser Dominic
Published: February 2024

The use of organic molecules as novel electrode materials potentially paves the way for the design of better and more sustainable batteries. Herein, the successful synthesis and comprehensive characterization of the alkali perylene tetra-carboxylate derivatives PCT-Li4, PTC-Na4, and PTC-K4 is reported. These conjugated carbonyl compounds are among the most promising organic electrode materials at present, since they can achieve high energy and power density as well as very good cycling stability. All materials were electrochemically tested vs. Li, Na, and K metal electrodes. A capacity of up to 120 mAh g-1 matching a two-electron redox reaction was obtained in all cases. The “crossover tests” with charge carriers not present in the pristine molecules demonstrate the great versatility of such materials. Moreover, ex situ FT-IR and operando XRD measurements were conducted to gain a deeper understanding of the influence not only of the charge carrier, but also of the initial crystal structure on the different charge storage mechanisms, as simulations for PTC-Li4
vs. Li indicate a decisive role of the initial crystal structure and, thus, contribute to the further development of organic batteries.

References

Dühnen, S. et al. Toward Green Battery Cells: Perspective on Materials and Technologies. Small Methods
4, 2000039 (2020).

Song, Z. & Zhou, H. Towards sustainable and versatile energy storage devices: an overview of organic electrode materials. Energy & Environmental Science
6, 22 80–2301 (2013).

Iordache, A. et al. From an Enhanced Understanding to Commercially Viable Electrodes: The Case of PTCLi4 as Sustainable Organic Lithium-Ion Anode Material. Advanced Sustainable Systems
1, 1600032 (2017).
Influence of Salt Concentration on Electrochemical Stability Window in Aqueous Electrolytes
Authors: Wahab Abdul , Pfeifer Rene , Zafar Zahid Ali , Cervenka Jiri
Published: February 2024

The thermodynamic limit of water electrolysis restricts the output voltage of aqueous metal ion batteries (MIBs) due to the low electrochemical stability window of water (1.23 V) in dilute electrolytes. It occurs due to the electrolysis of free water molecules into O2 or H2. Such value is unfortunately too low for many applications. For effective utilization of this technology, the ESW needs to be expanded to at least 2 V to achieve high energy density in metal batteries. Interestingly, water electrolysis can be suppressed by binding free water content with high concentrations of salts in highly concentrated water-in-salt electrolytes.

In this work, low-cost non-flammable aqueous Zn(ClO4)2 electrolytes have been studied for their electrochemical behaviour at different concentrations. The electrolytes have been evaluated via Raman spectroscopic analysis to examine the modification in local water structures associated with increasing salt concentration. We also used linear sweep voltammetry on a glassy carbon electrode to determine the electrochemical stability window of the electrolytes. Electrochemical results indicate the existence of two distinct regions in the concentration behavior of the onset potential for oxygen evolution reaction (OER) at a cut-off current density of 0.1 mA cm-2. In dilute electrolytes, the overpotential in OER increases with a low slope with increasing concentration, while there is a sharper overpotential increase at higher salt concentrations in the water-in-salt electrolytes. Raman spectroscopic analysis provides evidence of this electrochemical stability expansion as being a result of the disruption of the hydrogen bonding network present in pure water. A more compact and strongly coordinated ion hydration structure occurs in the water-in-salt electrolytes. In this way, a significant increase in oxidative stability and a decline in the Zn oxidation overpotential has been achieved in the highly concentrated water-in-salt electrolytes. Our results indicate that the Zn(ClO4)2 water-in-salt electrolytes offer more efficient Zn redox reactions and a higher electrochemical stability window than the diluted aqueous electrolytes, which is particularly beneficial for the development of high-voltage aqueous Zn ion batteries [1].

References

[1] Z. A. Zafar, G. Abbas, K. Knížek, M. Šilhavík, P. Kumar, P. Jiříček, J. Houdková, O. Frank, J. Červenka, J. Mater. Chem. A
10 (2022) 2064-2074.
Engineering Block Copolymer-Derived Porous Carbon Nanofibers as Anodes for Sodium Ion Batteries
Authors: Gordon Kenneth , Romero Cameron Taj , Liu Zhi , Usie Griffin , Joseph Karius , Broussard Emily , Fei Ling
Published: February 2024

For decades, lithium-ion batteries have seen widespread usage in a variety of applications from consumer electronics such as smartphones to the more recent developments of electric vehicles. As the usage of lithium for batteries increases, one growing concern is the finite amount that could be found within the Earth’s crust. An alternative that is being considered is sodium-ion batteries due to how plentiful sodium is in the Earth’s crust and similar chemical properties to lithium. One of the main challenges of sodium-ion batteries is the development of anode materials because sodium does not intercalate well with graphite, which is one of the most used materials in lithium-ion batteries. One promising development for anode materials is the use of hard carbon derived from the pyrolysis of polymers such as polyacrylonitrile (PAN) which can have various morphologies and potential for doping. Our work will focus on carbon nanofibers which show high 1-dimensional transport capabilities. With the addition of a sacrificial material such as polymethylmethacrylate (PMMA) that will be removed entirely during the pyrolysis step, PAN/PMMA can be made into porous carbon nanofibers to further increase ion transport. When a PAN/PMMA blend is used, the pores are very random with a high degree of variation of pore characteristics, however studies have shown that the creation of a PAN-b-PMMA block copolymer would allow for more uniform pore structures. Our work intends to study the effects of pore structures on the electrochemical characteristics of porous carbon nanofiber anodes for sodium-ion batteries. The cycling stability data of coin cells made using hard carbon nanofibers derived from electrospun PAN (Nonporous), PAN/PMMA (Random Porous), and PAN-b-PMMA (Uniform Porous), shows their respective discharging specific capacities (mAh/g) at 0.1 A/g average at about 80, 116, and 175. A slight increase can be seen with the addition of random, nonuniform pores to the PAN hard carbon, however, with the highly uniform and controlled pores resulting from the pyrolysis of the PAN-b-PMMA block copolymer, a very significant increase in the discharging specific capacity can be seen.
Electrodeposited Lithiophilic Zn Thin Film on the Current Collector for Improved Cyclability of Anode-Free Lithium Metal Battery
Authors: Afzali Pooria , Magagnin Luca
Published: February 2024

Anode-free lithium metal batteries (AFMBs) are recently presented as the new generation of Li metal batteries benefiting high gravimetric and volumetric energy densities due to the zero excess lithium. However, poor electrochemical stability and maximum cyclability of around 40-50 cycles due to the zero excess Lithium prevent the AFLMBs to be functional1. Here, lithiophilic electrodeposited Zn thin film on the current collector is reported in order to decrease the lithium nucleation overpotential and improve the plating/stripping process during alloying and dealloying. Moreover, columbic efficiency is increased by applying more zinc coated on the cupper current collector and by providing a more hospitable site for Li nuclei to plate2. Due to the alloy formation of Li-Zn, more conformal Li growth on the current collector is provided and homogeneous Li distribution and smooth morphology are observed by SEM images. The cells in different zinc thin layer coating are cycled with different current densities as well as long-term cycling by galvanostatic cycling charge-discharge cycling. As a result, increasing the thin film thickness up to 1 micron significantly enhances the electrochemical stability of the cells such as higher columbic efficiency and cyclability, lower Li nucleation overpotential. Finally, the Li-ion chemical diffusion coefficients DLi, are evaluated by galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) and the results are compared to each other3.

References

Maddukuri, S. et al. On the challenge of large energy storage by electrochemical devices. Electrochim Acta
354, 136771 (2020).

Merso, S. K. et al. An in-situ formed bifunctional layer for suppressing Li dendrite growth and stabilizing the solid electrolyte interphase layer of anode free lithium metal batteries. J Energy Storage
56, 105955 (2022).

Xie, J. et al. Determination of Li-ion diffusion coefficient in amorphous Zn and ZnO thin films prepared by radio frequency magnetron sputtering. Thin Solid Films
519, 3373–3377 (2011).
Heterointerface-Induced Fast Na+ Transport of Sn Anode Using a Yolk-Shell Structure for Fast-Charging and Stable Sodium-Ion Batteries
Authors: Lim Hyojun , Kim Sang-Ok
Published: February 2024

Sodium-ion battery (SIB) is a promising next-generation secondary battery system that uses inexpensive sodium resources, which can lower battery production costs. Moreover, based on similar chemical and electrochemical reaction mechanisms as conventional lithium-ion battery (LIB), it is expected that technology development can be rapidly achieved by utilizing existing battery manufacturing processes. However, because of the larger ionic radius (1.02 Å) and weight of sodium compared to those of lithium (0.76 Å), SIBs inevitably have lower energy and power densities compared to LIB. Therefore, to address these challenges, developing suitable host material with superior electrochemical performance (high capacity/high power density/long cyclability) is urgently required.

In this regard, metallic Sn has attracted attention as a promising anode material with a high theoretical capacity of 870 mAh/g through the reversible electrochemical (de)alloying reaction with sodium, which could overcome the low energy density limit of hard carbon anode. Nevertheless, due to the interfacial instability of Sn particles upon cycling and the slow alloying reaction rate during the sodiation process, the Sn anode exhibits poor rate performance and insufficient long-term cycling stability. Additionally, the structural degradation caused by significant volume variations further limits its practical implementation in SIBs.

Here, to solve the above issues, we propose a hierarchically designed composite anode consisting of Sn yolk and multifunctional C/SiOC shell (denoted as Sn@C/SiOC) via a simple pyrolysis method using the suspension of the Sn precursor in silicone oil. We conducted various physical, chemical, and electrochemical characterization, and we further carried out an in-depth investigation including post-mortem and in-situ EIS analyses to reveal the heterointerface-induced improved sodium-ion storage performance. We expect that the heterointerface modification strategy will contribute to the realization of advanced electrode materials in SIBs and other next-generation energy storage devices.
(Invited) Thermo-Photo Catalysis for Energy and Environment
Authors: Hu Yun Hang
Published: February 2024

Thermal heterogeneous catalysis based on kinetic energy as driving force was discovered in early 1800s, and photocatalysis using potential energy as driving force was introduced in 1911. Furthermore, catalysis driven by thermal energy generated from photo energy, which is actually thermal catalysis, also has a long research history. However, only in the past decade, we developed the thermo-photo catalysis, in which the synergy of thermal and photo energies drives a catalytic process. This new type of catalysis has been explored for various processes, including (1) water splitting to hydrogen, (2) dry reforming of methane, (3) steam reforming of methane, (4) partial oxidation of methane to value-added organic compounds, and (5) hydrogenation of CO and CO2 to hydrocarbons. These findings will be discussed in this presentation with emphasis on process design and catalyst development.
Visible Light Photocatalysis: Green Hydrogen Production
Authors: Alvarado-Ávila María Isabel , Ye Fei , Dutta Joydeep
Published: February 2024

The next few decades will experience the convergence of diverse materials and scientific disciplines resulting in innovative products and processes for the benefit of mankind. If the proliferation of today’s technologies and the urgent need to address global climate change issues is any indication of the speed and power of changes in economies to be expected, a dramatic shift to sustainable technologies has to occur to provide cost-effective, low carbon footprint solutions. In this talk we will introduce about possible strategies based on fundamentals of physics and materials engineering that can potentially contribute to our efforts to preserve the planet’s environment at an acceptable level. Exploiting solar energy, as visible radiation constitutes a major share (~ 46%) of the solar spectrum, strategies for carbon reduction technologies can be devised. We have been working on the synergistic development of visible light active photocatalysts suitable for activating reactions by engineering nanomaterials and interfaces. Hydrogen production (H2) by Photocatalytic reactions is a promising process for green H2 generation as a fuel or an alternate energy source. Organic compounds like alcohols, polyols, sugars, as well as organic acids and lignocellulosic compounds can serve as sacrificial agents (electron donors) to reduce e−–h+ recombination leading to a more efficient process. Cellulose, the most abundant material on the earth that is a part of some of the waste generated by humans is a natural and carbon-neutral source as a sacrificial agent during photo-induced splitting of water for green H2 production and can be an attractive for building a sustainable system for photocatalytic H2 production. Some of these areas utilising
visible light photocatalysis
for oxidation of organic pollutant, microbe removal, anti-biofouling coatings and microplastic degradation will be briefly discussed.
(Invited) High Efficiency, Ultra-Stable Solar Hydrogen Production
Authors: Mi Zetian
Published: February 2024

Solar water splitting and green hydrogen fuel production has been extensively studied but are confronted with fundamental challenges of simultaneously achieving both high efficiency and long-term stability. In this presentation, I will report on our recent developments of gallium nitride (GaN) based photoelectrochemical and photocatalytic water splitting studies. By growing GaN nanostructures under N-rich conditions, the surfaces can be transformed to be gallium oxynitride during harsh photocatalysis reaction, which not only further protects the surfaces of the light absorber but leads to significantly enhanced photocatalytic and photoelectrochemical performance. Moreover, we have developed unique photocatalytic process wherein high efficiency solar hydrogen can be produced utilizing tap water, or seawater, without any wire connection, or electricity input. The demonstration of large-scale solar water splitting systems and the performance will be discussed and reported.
MOCVD of ZrN: Tuning Thin Film Properties Towards Catalytic Applications
Authors: Glauber Jean-Pierre , Liu Ji , Lorenz Julian , Bragulla Sebastian , Müller Björn , Harms Corinna , Wark Michael , Nolan Michael , Devi Anjana
Published: February 2024

Transition metal nitrides (TMN) have gained increasing attention over recent years as active materials for energy related applications including catalysis and energy storage. They feature high electrical conductivities, wide optical band gaps and superior chemical stability.[1] In particular, ZrN has been recently identified as a promising material for a range of potential applications that include plasmonic devices,[2] as a catalyst for the oxygen reduction reaction (ORR),[3] and as a catalyst for the nitrogen reduction reaction (NRR),[4] due to its appealing electronic properties, while being cheap and abundant compared to commonly used noble metals.[1,5] The fabrication of ZrN on large scale under moderate process conditions, with the required properties for catalytic applications, motivates the use of chemical vapor deposition (CVD) as the method of choice. Moreover, with the variation of process parameters that includes precursor choice and growth temperature, it is possible to tune the surface features as well as composition of the layers that are suitable for catalytic applications.

In this study, we have employed metal organic chemical vapor deposition (MOCVD) to synthesize ZrN layers on Si and glassy carbon (GC) substrates in the temperature range of 550 – 850 °C. The influence of the nature of the precursor and deposition temperature on the structure, composition and surface morphology of the ZrN layers was systematically studied. Oriented ZrN layers with facetted grain morphology were obtained. ZrN films of different thickness were analyzed by complementary methods including X-ray diffraction (XRD) (Figure 1 a)), Raman spectroscopy, Rutherford backscattering spectrometry (RBS) (Figure 1 b)), nuclear reaction analysis (NRA), scanning electron microscopy (SEM) (Figure 1 c)), and X-ray photoelectron spectroscopy (XPS). Based on the detailed film analysis, catalyst surfaces were modeled by DFT calculations. The NRR activity and selectivity towards the competing hydrogen evolution reaction (HER) were evaluated by first principles simulations and electrochemical experiments. This preliminary study on material fabrication and theoretical investigations lays a foundation for the investigation of ZrN for NRR applications for future studies.

References:

[1]: Luo, Q.; Lu, C.; Liu, L.; Zhu, M., Green Energy &
Environ.
2023 8 (2), 406.

[2]: Shabani, A.; Tsegay K., M.; Petersen, S.; Khazaei N., M.; Kumar M., Y.; Adam, J., Adv Photo Res. 2021 2 (11), 2100178.

[3]: Yuan, Y.; Wang, J.; Adimi, S.; Shen, H.; Thomas, T.; Ma, R. et al., Nat. Mater.
2020, 19 (3), 282.

[4]: Abghoui, Y.; Garden, A. L.; Howalt, J. G.; Vegge, T.; Skúlason, E., ACS Catal.
2016 6 (2), S. 635.

[5]: Xie, J.; Xie, Y., Chemistry
2016, 22, 3588.

Figure 1
Hydrogen Evolution Using a Highly Efficient MoS2-Carbon Nano-Onion Heterostructure Electrocatalyst
Authors: Shim Jae-Jin , Parasseeri Muhammed Shafi , Al Mahmud Abdullah
Published: February 2024

Hydrogen, a clean and sustainable energy source, can be produced by electrochemical water splitting using an electrocatalyst. However, developing an inexpensive, efficient catalyst for hydrogen evolution reaction (HER) is a challenge as it is difficult to obtain an electrocatalyst with a large accessible active surface. In this study, a sulfide of a non-noble metal, molybdenum, was employed as an electrocatalyst. Due to the restacking of 2D MoS2 layers, access to the active area was limited. This drawback of the 1T MoS2 catalyst was overcome by incorporating the carbon nano-onion (CNO). The unique MoS2-CNO heterostructure formed by growing a few-layered 2D 1T MoS2 on the CNO core facilitated smooth and barrier-free charge transfer through the heterojunction formation. This heterostructure mitigated restacking and maintained structural stability, providing a long-term high-performance catalyst. This MoS2-CNO exhibited an excellent HER performance with an overpotential of 53 mV vs. RHE and a Tafel slope of 40.8 mV dec-1 for over 25 h, showing it one of the best HER catalysts, next to platinum. This study highlights a new, highly stable, highly performing non-noble metal catalyst for electrochemical water splitting applications.
(Invited) Organic Polymer Dots for Photocatalysis
Authors: Tian Haining
Published: February 2024

Organic polymeric photocatalysts have been attracted scientists’ interests during past years due to their low-cost, tunable bandgaps and energy levels, and promising photocatalytic performance. Making the traditional hydrophobic polymeric photocatalyst into nano-particles with size less than 100 nm, so-called polymer dots (Pdots), has shown significantly enhanced photocatalytic activity. Rational design of organic polymers is one of strategies to improve photocatalytic performance for hydrogen production. Moreover, making heterojunction Pdots can efficiently separate photogenerated charges within Pdots as well as utilize energy transfer process to enhance the light harvesting efficiency. In this talk, I will discuss our research achievements in optimization of polymer structures on Pdots photocatalysis, study of photocatalytic mechanism in heterojunction Pdots systems and applications of Pdots in bio-hybrid photocatalytic systems.

Relevant publications:

[1] Wang L., et al., Angew. Chem., 2016, 128 (40), 12494-12498

[2] Pati P., et al., Energy Environ. Sci., 2017 10 (6), 1372-1376

[3] Liu A., et al., J. Am. Chem. Soc., 2021, 143 (7), 2875-2885

[4] Pavliuk M., et al., J. Am. Chem. Soc. 2022, 144(30) 13600–13611

[5] Wang S., et al., Angew. Chem. Int. Ed., 2022, 61(23), e202202733
Post-Synthetic Modifications of Ti(IV)-Based Metal-Organic Frameworks for Enhanced Photocatalysis and Conductivity
Authors: Kissel Daniel
Published: February 2024

Metal-Organic Frameworks (MOFs) are coordination networks with organic ligands containing potential voids, ideal for guest-host interactions. These unique characteristics make them interesting materials for several different applications, including catalysis. Unfortunately, most MOFs feature metal oxide nodes that are insulting by nature, which limits their potential in electro- and photochemical catalysts. To combat these issues, post-synthetic modifications (PSM) can be used to tune MOF properties. This research reports on different PSMs incorporated into the Ti(IV)-based MOFs MIL-125(Ti) and MIL-125(Ti)-NH2. PSMs that introduce intentional defect states and dopant metal ions, such as Ce(IV), were explored to determine their influence on the photo-degradation of Rhodamine B in aqueous solution. Post-Synthetic Metal Exchange (PSME) was used to incorporate Ce(IV) at the Ti(IV) sites in MIL-125(Ti) and MIL-125(Ti)-NH2, and intentional defect states were introduced using formic acid during MOF synthesis. In addition, conductive organic polymers were utilized to make novel polymer-MOF hybrid composites that showed enhanced charge transport properties compared to pristine MOF. Ultimately, these results show how PSMs can be used to impart conductivity and enhance photocatalysis in the MOFs MIL-125(Ti) and MIL-125(Ti)-NH2.
Solar Water Splitting Device Integrated Carbon-Based Electrodes and Carbon-Based Perovskite Solar Cells
Authors: Tsuji Ryuki , Ito Seigo
Published: February 2024

Producing hydrogen from integrated devices by solar-driven water splitting (SWS) is one of the most attractive methods for renewable energy conversion. However, their widespread use is hindered by their cost and poor performance. In this work, we developed an integrated device consisting of three series-connected carbon-based multi-porous-layered-electrode perovskite solar cells (MPLE-PSCs) 1-5 and carbon-based catalyst-decorated electrode couples (Figure 1a). Porous carbon electrodes with a graphite and carbon black mixture are used for the back contacts of solar cells, and pencil-lead graphite rods (PGRs) are used as electrocatalyst supports for water-splitting cells, which are much cheaper than existing materials. The performance of the PSC was compared between the 2 and 3-series, and the performance of the water-splitting cell with/without catalyst. In addition, each combination was compared.

The solar to electricity efficiency (STE, same as power conversion efficiency: PCE) was 13.79% and 13.16% for the 2-series and 3-series, respectively. The electricity to hydrogen efficiency (ETH), calculated as V
theoritical/V
operating, 6 was 78.34% and 84.83%, for PGR and NiFe/PGR respectively. Furthermore, the matching factor (MF), calculated as (V
operating × J
operating)/(V
max × J
max), 6 for the <2-series PSCs>/ combination and the <3-series PSCs>/ combination were 48.57% and 83.77%, respectively. Solar to hydrogen efficiency (STE), calculated as STE ×ETH × MF, improved from 5.25% to 9.35% for the optimized device (Figure 1b). These results show that low-cost and high-efficiency solar hydrogen can be produced by using Earth-abundant materials and by adjusting the maximum output of the device.

(1) A. Mei, et al., Science
345, 295 (2014).

(2) R. Tsuji, et al., Electrochemistry
88, 418 (2020).

(3) R. Tsuji, et al., Photonics
7, 133 (2020).

(4) D. Bogachuk, R. Tsuji, et al., Carbon
178, 10 (2021).

(5) E. Kobayashi, R. Tsuji, et al., Cell Rep. Phys. Sci.
2, 100648 (2021).

(6) Z. N. Zahran, et al., ACS Appl. Energy Mater.
5, 8241 (2022).

Figure 1. Carbon-based solar water splitting. (a) Schematic diagram and (b) J-V curves of MPLE-PSCs and LSV curves of water electrolysis with PGR electrodes.

Figure 1
(Invited) Selective and Efficient Electrochemical CO2 Reduction Reaction from Cu and Cu-M Binary Alloys
Authors: Oh Jihun
Published: February 2024

Electrochemical CO2 reduction reaction (CO2RR) has attracted a great deal of attention due to its potential to convert CO2 into valuable chemical fuels and feedstocks. The production of C2+ chemicals, such as ethylene and ethanol, from CO2RR is particularly important because of their large market demand. However, several challenges must be addressed before CO2RR can be commercially scaled up, including high overpotential, low selectivity, and poor CO2 solubility in aqueous solutions. In this presentation, I will discuss our recent efforts to overcome these challenges in CO2RR by using a gas diffusion electrode (GDE) to achieve a CO2RR current density of over 100 mA/cm2 in a flow reactor. First, I will highlight the crucial role of the local CO2RR environment in promoting C-C coupling on Cu surfaces, and I will present strategies for controlling this environment based on steady-state modeling and monodisperse Cu2O nanoparticles as a model catalyst system. Using this approach, we have been able to produce C2+ products, such as ethylene and ethanol, with a Faraday efficiency of over 70% at a current density of over 300 mA/cm2 in near-neutral electrolytes. Additionally, I will discuss the impact of alloying Cu with Ni and Zn on tailoring product selectivity. By introducing elements with different CO binding strengths, we can significantly alter the selectivity for hydrocarbons and alcohols. I will provide further details on these findings during the presentation.