bluuebunny/crossref_metadata_2025_split huggingface dataset:
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.
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).
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.
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
Photo-Generated Charge Carrier Dynamics in Metal Oxide Photocatalysts
Authors: Tachibana Yasuhiro 
Published: February 2024

Solar water splitting is one of the most attractive energy carrier generation processes to utilize solar energy. Light generated hydrogen is a clean energy carrier, since their consumption for energy generation produces only water. Moreover, generated hydrogen can be stored and used whenever required. Hydrogen is mostly used as a feedstock in the chemical and petrochemical industries, e.g. production of ammonia, methanol and fertilisers.[1]
The photocatalytic solar water splitting process has been studied extensively over the last half century. However, despite the efforts, no ideal photocatalyst has yet been identified to meet three main requirements for commercialisation: (1) low cost, (2) high solar to hydrogen (STH) efficiency and (3) durability. Over the last two decades, considerable efforts have focused on developing visible light active photocatalysts, and some promising photocatalysts with relatively high water splitting efficiency were discovered.[2] In contrast to search of appropriate photocatalyst (nano)materials, mechanisms of photocatalytic water splitting reactions, in particular charge carrier dynamics of photocatalysts, were little studied. Understanding charge carrier dynamics in photocatalysts will certainly provide an opportunity to design high efficiency photocatalysts.
In this presentation, we will show dynamics of photo-generated charge carries in metal oxide photocatalyst by employing a series of transient absorption spectroscopies covering from 150 fs to 100 s over UV-VIS-NIR wavelength ranges.[2] Correlation of the charge carrier dynamics with photocatalysis reactions will be discussed.
This work was partly supported by ARC DP fund (DP180103815) and ARC LIEF funds (LE170100235 and LE200100051), Australia, and the Collaborative Research Program of Institute for Chemical Research, Kyoto University (grant number 2023-45 and 2022-99), Japan. We also acknowledge supports from School of Engineering, RMIT University, and Forefront Research Center, Faculty of Science, Osaka University.

References

[1] N. Armaroli and V. Balzani, ChemSusChem
4 (2011) 21-36.
[2] H. Mai, D. Chen, Y. Tachibana, H. Suzuki, R. Abe, Rachel A. Caruso, Chem. Soc. Rev., 50(24) 13692-13729 (2021).
[3] H. Liu, M. Liu, R. Nakamura, Y. Tachibana, Appl. Catal. B-Environ., 296 (2021) 120226.
(Invited) Mulitjunction III-V Semiconductors for Photo-Electrochemical Hydrogen Production: Recent Progress in Efficiency, Durability, and Cost
Authors: Deutsch Todd G , Wyatt Keenan , Steiner Myles A. , Young James L. 
Published: February 2024

Photo-electrochemical (PEC) hydrogen production is a route to carbon-free fuel that combines light absorption and water electrolysis into one device. Challenging targets for solar-to-hydrogen (STH) efficiency, durability, and semiconductor absorber costs must be realized for this approach to be economically competitive with other hydrogen production pathways. Research on PEC hydrogen production at the National Renewable Energy Laboratory (NREL) has focused on III-V semiconductor absorber materials because their tunable bandgaps, high photon conversion efficiencies, and ability to make multi-junction structures have resulted in the highest STH efficiencies yet demonstrated.
This talk will focus on recent NREL results showing progress toward PEC hydrogen production efficiency, durability, and cost targets. Specifically, we have been able to improve theoretically achievable STH efficiency through bandgap engineering in multijunction devices. Photon management strategies to close the gap between theoretical and measured STH efficiency will also be discussed. Durability remains a significant challenge for III-V materials in a PEC environment. We will describe modifications to the semiconductor surface and the electrolyte constitution that can make the photoabsorber less susceptible to photocorrosion during operation. Finally, we will present preliminary results on III-V PEC materials synthesized via hydride vapor phase epitaxy, an alternative route to high-efficiency photoelectrodes that could potentially have much lower costs than the metalorganic vapor phase epitaxy method traditionally used. These improvements have yielded III-V PEC devices that are close to the STH efficiency target (17% vs. 25%) while the demonstrated durability and cost are still considerably far from their target values.
Solar Hydrogen Production and Biomass Reforming Using Earth-Abundant Non-Toxic Si-Based Photocatalysts
Authors: Ryu Jungki 
Published: February 2024

The efficient production of electrochemical hydrogen and biomass refinement is crucial for the decarbonization of various industries. However, their low efficiency and high energy requirements make them impractical. In this talk, we propose using earth-abundant and non-toxic photocatalysts that can produce hydrogen and reform biomass efficiently by utilizing solar energy. Our approach involves using low bandgap Si flakes (SiF) for efficient light absorption. SiF was further modified with Ni-coordinated N-doped graphene quantum dots (Ni-NGQDs) to enable stable light-driven biomass reforming and hydrogen production. SiF/Ni-NQGDs enabled a record hydrogen productivity and concurrent vanillin production when using kraft lignin as model biomass under simulated sunlight without any buffering agent or sacrificial electron donors. SiF/Ni-NQGDs can also be easily recycled without noticeable performance degradation due to the prevention of Si deactivation through oxidation. Our findings provide valuable insights into the practical application of biomass refinement and electrochemical hydrogen production and efficient use use of solar energy.
Reference)
1. Y. Choi, S. Choi, I. Lee, T. V. T. Nguyen, S. Bae, J. Ryu, Y. H. Kim, S. Park, J. Ryu, Solar Biomass Reforming and Hydrogen Production with Earth-Abundant Si-Based Photocatalysts. Advanced Materials
2023, Accepted.

Figure 1
(Invited) Stabilization and Activation of Copper(I)-Oxide-Semiconducting Interfaces for Photoelectrochemical Reduction of Carbon Dioxide
Authors: Kulesza Pawel J. , Rutkowska Iwona A. 
Published: February 2024

Electroreduction of carbon dioxide to simple organic fuels and chemicals is a topic of growing scientific and technological interest. The reaction provides means for both reducing emissions of CO2 into atmosphere and storing renewable energy. The presentation will address low-temperature CO2-conversion processes based on electrocatalytic and photoelectrochemical approaches. Among important issues are choice of the catalytic or semiconducting materials, their morphology and operating conditions including temperature, solvent, electrolyte, pH etc. There is a need to improve the reaction dynamics and selectivity toward specific products. In practical electrolysis cells, the CO2-reduction (at cathode) is accompanied by water oxidation (at anode or photoanode).
Recently, we have concentrated on the development of hybrid materials by utilizing combination of metal oxide semiconductors thus capable of effective photoelectrochemical reduction of carbon dioxide. For example, the combination of conducting polymers, or titanium (IV) oxide, and copper (I) oxide has been considered before and after sunlight illumination. Application of the hybrid system composed of both above-mentioned oxides resulted in high current densities originating from photoelectrochemical reduction of carbon dioxide mostly to methanol (CH3OH) as demonstrated upon identification of final products. Among important issue is intentional stabilization, activation, and functionalization of the mixed-metal-oxide-based photoelectrochemcal interface toward better long-term performance and selectivity production of small organic molecules (C1-C4) and other chemicals. In this respect, ultra-thin films of conducting polymers (simple or polyoxometallate-derivatized) and supramolecular complexes (with nitrogen containing ligands and certain transition metal sites), sub-monolayers of metals (Cu, Au), networks of noble metal (Au, Ag) nanoparticles or layers of robust bacterial biofilms have been considered. The photobiocathode utilizing robust biofilms have also been demonstrated to stabilize copper(I) oxide surfaces and to induce the system’s activity toward reduction of carbon dioxide under illuminations with visible light.
In the presentation, special attention will be paid to the mechanistic aspects of electroreduction of carbon dioxide, fabrication and characterization of highly selective and durable semiconductor photoelectrode materials and to the importance of the reaction conditions.