bluuebunny/crossref_metadata_2025_split huggingface dataset:
Partial Replacement of Manganese in Sodium Manganese Hexacyanoferrate for Long-Life Sodium-Ion Cathode Materials
Authors: Buechele Sebastian , Binder Joachim R. 
Published: February 2024

Among the various cathode active materials for Na-ion batteries Prussian Blue Analogs (PBA) are a promising candidate. From a cost and sustainability perspective, Na2Mn[Fe(CN)]6 (NaMnHCF) is of particular interest due to its high potential and superior electrochemical performance.[1] However, it suffers from poor cycling stability which is believed to be partly due to structural distortions caused by the Jahn-Teller effect of oxidized Mn3+ and dissolution of Mn in the electrolyte.[1,2] An alternative PBA like Na2Fe[Fe(CN)]6 (NaFeHCF) does not have these issues, but operates at a lower average potential of about 3.15 V versus Na+/Na during discharge (versus 3.45 V for NaMnHCF).[3]

Therefore, in this study, the systematic replacement of Mn is investigated to find an optimum of high potential and good cycling stability.[4] As an example, Figure 1 shows the voltage curves for the first C/20 cycle in sodium half cells with Na2Mn[Fe(CN)]6 (green) or Na2Mn0.8Fe0.2[Fe(CN)]6 (blue). The material with the higher Fe content clearly shows a second, lower plateau and an overall lower potential.
The materials were compared in terms of their electrochemical properties and characterized by SEM, XRD, ICP-OES and TGA.

References

Song, J., Wang, L., Lu, Y., Liu, J., Guo, B., Xiao, P., ... & Goodenough, J. B. (2015). Journal of the American Chemical Society, 137(7), 2658-2664.

Xu, C., Ma, Y., Zhao, J., Zhang, P., Chen, Z., Yang, C., ... & Hu, Y. S. (2023). Angewandte Chemie International Edition, 62(13), e202217761.

Wang, L., Song, J., Qiao, R., Wray, L. A., Hossain, M. A., Chuang, Y. D., ... & Goodenough, J. B. (2015). Journal of the American Chemical Society, 137(7), 2548-2554.

Chen, X., Xia, Y., Fang, X., Zhang, K., Xiong, Y., & Jian, Z. (2022). Journal of Materials Science, 57(29), 14015-14025.

Figure 1
Improving Cycle Stability and Kinetics of Rechargeable Al/CO2 Batteries By Functional Cathode Materials
Authors: Diaz Gustavo , Fetrow Christopher , Vadthya Raju , Wei Shuya 
Published: February 2024

Metal-CO2 batteries have emerged as a promising solution for advancing energy storage technology and sequestering carbon dioxide from ambient air. Aluminum (Al) is an appealing anode material for electrochemical CO2 capture and conversion due to its lower cost and reactivity in comparison to lithium and sodium anode materials, making it safer and more accessible for manufacturing. Its abundance across various regions of the world further adds to Al’s attractiveness. Additionally, Aluminum boasts a high specific energy of 2980A·hour/kg, suggesting that its electrochemical conversion with CO2 can produce large amounts of electrical energy. Previous study shows that Aluminum/CO2 batteries possess a remarkable discharge capability with the introduction of a small amount of oxygen, however, these batteries are not rechargeable.
By utilizing a homogeneous iodine-based redox mediator, our group demonstrated that the Al-CO2 battery can achieve reversible discharge and charge with minimal overpotential of 0.05V, reducing stripping/plating overpotentials by 40% across various current rates compared to an unmodified imidazolium-based ionic liquid electrolyte. This is achieved by replacing oxygen gas with aluminum iodide in the electrolyte, which maintains high discharge capacity and enables the battery to be recharged for up to 12 cycles at a 20 mA/gcarbon rate.
Examining the discharge and charge rates of different cathode materials was necessary to demonstrate the improvement in cycle stability. By utilizing functional carbon-based materials with increased surface area, heteroatom doping and unique pore structure as the cathode, we demonstrate that the rechargeable Al-CO2 battery can enhance CO2 reduction during the discharge processes, thereby improving reaction kinetics.
Higher surface area and porous materials facilitate faster electron transfer during the electrochemical reactions while allowing better CO2 diffusion into the cathode, improving reaction rates.
(Invited) Understanding and Controlling Electrolyte Solvation-Stability Relationships Toward Energy Dense Multivalent Batteries
Authors: Hahn Nathan T. 
Published: February 2024

High energy density multivalent batteries, primarily those based on Mg or Ca metal anodes, have remained theoretically promising but practically elusive for many years. Simultaneous development of novel electrolytes and cathode materials has been undertaken across the globe in an attempt to make such batteries practical. However, a relative dearth of effective solid-electrolyte-interphase (SEI) chemistry in these systems imposes stability challenges for the electrolyte at the strongly reducing metal anode and strongly oxidizing transition metal oxide cathode interfaces. Therefore, electrolyte advances have been driven primarily by the utilization of constituents having exceptional reductive and/or oxidative stability. Addressing these intrinsic stability criteria are, however, only half the battle; the solvation interactions of these constituents with the strong Lewis acid working cations and the resultant stability effects must be considered as well.
In this presentation I will describe recent insights and approaches in Mg and Ca battery electrolyte design from the solvation science perspective incorporating both theory and experiment. I will focus especially on strategies for managing solvent-cation interactions to achieve electrolyte stability toward both anodes and cathodes. From this discussion, I will provide some perspective on opportunities and considerations for future advancement in multivalent (or other) battery electrolytes.
Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
Challenges and Breakthroughs Towards the Development and Optimisation of a Zero Excess Li-S Battery
Authors: Cruddos Joshua , Rettie Alex J.E. 
Published: February 2024

There is currently a large demand to produce batteries and energy storage devices offering both improved volumetric and gravimetric energy densities to help prevent the catastrophic effects of climate change. One promising candidate is the lithium-sulfur (Li-S) chemistry due to the high theoretical capacity and abundance of sulfur. However, current designs require a 1000% excess of Li metal which impedes their commercialisation. An area gaining momentum is the development of “anode-free” or zero excess lithium (ZEL) cells which minimise inactive materials and mitigate the challenges of handling Li metal foils during fabrication. So far, most studies involving anode-free have been based on the Li-ion chemistry and there are significantly fewer systematic studies concerning ZEL Li-S cell fabrication and optimisation. However, nearly all fall short of targets required for commercialisation.
Here we present the development of an Li2S ZEL cell composed of a Li2S/C65/SBR positive electrode material paired with a metallic current collector. The design allows for a Li-limited LiS battery where Li-ions are reversibly plated and stripped to a metallic current collector surface. We initially investigate the effects of electrolyte
volume
:Li2S
mg
(ES) ratio, conductive carbon loading, C-rate capacity dependency, various current collector materials and positive electrode substrates. The optimised cell achieves good capacity retention with a Coulombic efficiency of over 98% after 50 cycles, and a final capacity of 400 mAh g-1.
Previous studies have shown difficulties in achieving consistent results and are often distorted by a large volume of conductive carbon present in the cathode substrate [1, 2]. Therefore, investigations into capacity losses stemming from the cathode are presented using a range of air-tight characterisation techniques. The performance is also closely correlated to the efficiency of reversible Li deposition onto the metallic current collector, as evaluated by comparison to the use of Li negative electrodes. In the ZEL set up, losses from dead Li formation and SEI instability result in permanent loss of Li inventory with no reservoir to replenish. To counter this, initial investigations attempting to apply an ionically conductive coating to the metal current collector surface are shown.
[1]. S. Nanda, A. Gupta and A. Manthiram, Adv. Energy Mater., 2018, 8, 2–7.
[2]. S. Nanda, A. Bhargav and A. Manthiram, Joule, 2020, 4, 1121–1135.
Lithium Magnesium Alloys: A Framework for Investigating Lithium Alloy Anodes for Solid State Batteries
Authors: Aspinall Jack , Sada Krishnakanth , Guo Hua , Narayanan Sudarshan , Chart Yvonne , Jagger Ben , Milan Emily , Armstrong David , Pasta Mauro 
Published: February 2024

Lithium alloys have the potential to overcome anode-side challenges in solid state batteries. In this work we synthesise and characterise lithium-rich magnesium alloys, quantifying the changes in mechanical properties, transport, and surface chemistry that impact electrochemical performance. Increases in hardness, stiffness, adhesion, and creep are quantified by nanoindentation as a function of magnesium content. A decrease in diffusivity is quantified with chronopotentiometry and 6Li PFG-NMR, and an increase in interfacial impedance due to the presence of magnesium is identified with electrochemical impedance spectroscopy which is correlated with XPS data. Throughout, changes in properties are linked to electrochemical performance. This work provides a framework to investigate other lithium alloy systems.
Jack Aspinall et al. Lithium magnesium alloys: a framework for investigating lithium alloy anodes for solid state batteries, 16 March 2023, PREPRINT (Version 1) available at Research Square [https://doi.org/10.21203/rs.3.rs-2688902/v1]
Dr. Virkar's Self-Reflections on Research Career
Authors: Virkar Anil 
Published: February 2024

I have been helped by many mentors and mentees. My greatest mentor has been my father, who received PhD in organic chemistry in 1942, more than two years before I was born. That made both my brother (who has a PhD in mathematics) and myself pursue higher education. I have been immensely helped by many mentors. I will briefly talk about them.
At Northwestern University, Prof. Morris E. Fine, who was not my advisor, but had a profound influence on me. His dedication to work is unparalleled. He retired at age 65 (as was the case then) but continued as Professor Emeritus until his death at the age of 97. It was amazing for me to see that he went to work at least 3 days a week well into his 90’s. One week, he did not come, so people from the MSE department at Northwestern went to his house, only to find that he had passed away in his sleep.
I came to Utah in September 1973, as a post-doctoral fellow, working for Prof. Ronald S. Gordon, on sodium-sulfur batteries. I was hired to measure strength of Na-beta”-alumina ceramics. He had been my mentor for over 35 years, and passed away in 2008. He gave me many opportunities, and was instrumental in my getting a faculty position at Utah. He also founded Ceramatec, which provided jobs to hundreds over the years. He was one of the closest friends I have had in my life. During my early career, Prof. Richard H. Boyd, Chair of MSE, helped me enormously. He gave me various courses to teach; from the basic MSE course to statistical thermodynamics. I can say without hesitation that it helped me develop various areas of research; basically, my teaching drove my research, rather than the other way around, which is often the case.
I have been extremely fortunate to have had excellent students working in my group over the years; they include Bill Rafaniello, L. Viswanathan, Tom Yuan, Gajavalli Srinivasan, Peter Kuo, Jong Chen, Jow-Lay Huang, Quing Tian, Cameron Tanner, Srikanth Gopalan, S-J.Hong, Pomin Su, Jan-Fong Jue, R. Ganeshananthan, Lei Zhang, Alex Szendrei, Kuan-Zong Fung, Seong J. Kim, Hyung D. Baek, Hyung-Tae Lim to name a few, and post-doctoral fellow Liangzhu Zhu, among others. The list is by no means complete.
On the technical part, I will talk about what significant changes occur to yttria-stabilized zirconia during electrolysis and the need to conduct property measurements after electrolysis. I have worked on many research topics over the years. The most recent efforts have been on the application of Onsager equations to solid electrolytes.
(Invited) Ceramic-Based Electrochemical Systems for Sustainable Transition to Zero-Carbon Energy
Authors: Gür Turgut M. 
Published: February 2024

Realizing a sustainable energy future pose multiple challenges, especially with respect to our heavy dependence on fossil fuels. In that regard, electrochemical energy conversion systems based on ionically and mixed conducting ceramics offer unique opportunities for clean energy production from fossil fuels by abandoning the undesired air-based combustion that emits CO2 into the atmosphere and replacing it with oxygen-based electrochemical conversion processes, which produce capture-ready CO2 instead and avoid emissions. In the context of climate change, this distinction is critically important as processes that release CO2 unabatedly into the atmosphere must be avoided entirely. But that does not necessarily require that we should rush to abandon fossil fuels prematurely before we can replace them at-scale with clean energy alternatives.
After framing the global energy landscape and threats to climate change, this presentation will discuss the opportunities and technical challenges of converting fossil fuels in solid oxide-base fuel cells with focus on solid fuels including coal. It will also introduce the new concept of electrochemical gasification to produce ‘blue’ hydrogen from fossil fuels without release of CO2 into the atmosphere. These technologies can help avoid major disruptions to energy supply and offer a smooth transition into a zero-carbon energy economy.
(Invited) On Non-equilibrium Thermodynamics in Electrochemical Systems
Authors: Zhou Xiao-Dong 
Published: February 2024

Much of our understanding of physical behavior of materials is based on the concept of equilibrium, which lies at the heart of classical thermodynamics, condensed matter physics, and modern reaction kinetics. If a thermodynamic system is in equilibrium conditions, which is the situation when an energy system (e.g., a fuel cell or a battery) is under open circuit voltage, the surface and bulk of the electrode are only subject to fluctuation of thermodynamic qualities. For the cases that are not at equilibrium, but are close to it, Onsager established linear reciprocal relationships between flux and thermodynamic force for a thermodynamic system in nonequilibrium states. These linear relationships are manifested in transport phenomena, which are non-equilibrium processes, such as ion diffusion and heat conduction.
When an electrochemical reaction takes place at an electrode of a fuel cell, electrolyzer, or battery, the thermodynamic system is far away from equilibrium. Therefore, the thermodynamic states of the surface and bulk of an electrode are subject to external thermodynamic forces. As a result, in an active electrode, the electrochemical reaction on the surface causes all thermodynamic variables to change in both the surface and the bulk. In this talk, I will use solid oxide cells and lithium-ion batteries as an example to address three questions related to materials in non-equilibrium thermodynamic states: (i) how do fast kinetics and high current in an operating electrochemical cell affect the thermodynamic states of its material constituents, (ii) whether or not the state of non-equilibrium can remain stable with constant flow of matter and energy, and (iii) what is the origin that governs activity and stability in solid oxide cells?
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).
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.