bluuebunny/crossref_metadata_2025_split huggingface dataset:
Solution-Processed Non-Crystalline Solid Electrolytes for Advanced Energy Storage
Authors: Rettie Alex J.E. 
Published: February 2024

Advanced batteries containing a Li metal anode (LMA) are needed to enable the clean economy and meet ambitious climate targets. Currently, LMA batteries are limited by dendrite propagation due to the non-uniform plating and stripping of Li, which is detrimental to cell performance. The non-crystalline solid electrolyte (SE), lithium phosphorus oxynitride (LiPON) is unique in demonstrating stable Li plating/stripping at appreciable rates, but its synthesis requires costly and slow vacuum deposition methods. We use aqueous precursor solutions which are rapidly condensed during spin coating and gently annealed to produce dense, flat, Li metal oxide films without long-range order. However, such solution-processed SEs typically exhibit ionic conductivities (σ
ion
) too low for energy storage applications (~10-8 S cm-1) and far lower than vacuum-deposited LiPON (~10-6 S cm-1).
We will discuss various approaches to increase the σion of these materials, including compositional engineering and controlled processing conditions. Structure-property relationships have been elucidated using modelling of the local structure and interphase formation against Li evaluated by time-dependent electrochemical impedance spectroscopy and in situ X-ray photoelectron spectroscopy. Electrochemical testing of these films deposited onto a current collector in an anode-free cell will be used to evaluate their ability to facilitate stable deposition and stripping of Li.
Initial exploration of processing parameters have yielded σion values > 10-7 S cm-1 [1] and the presence of medium-range order (nanocrystalline domains) in some cases. Beyond Li, new non-crystalline SEs for other ions will be discussed. As only limited chemical compositions and processing conditions of these materials have been reported, with no corresponding structural studies, our work provides insight to enable the optimisation and discovery of scalable non-crystalline SEs for advanced batteries.
1. P. Vadhva, T. Gill, J. H. Cruddos, S. Said, M. Siniscalchi, S. Narayanan, M. Pasta, T.S. Miller, A.J.E. Rettie. Engineering solution-processed non-crystalline solid electrolytes for Li metal batteries. Chemistry of Materials, 2022, 35, 3, 1168–1176.
Hierarchically Structured Potassium-Vanadium-Phosphate/C Composites As Possible High-Voltage Cathodic Materials for Potassium-Ion-Batteries
Authors: Heyn Andreas , Jeschull Fabian , Binder Joachim R. , Bohn Nicole 
Published: February 2024

Potassium-ion-batteries (PIBs) share technological similarities with Lithium- and Sodium-ion batteries (LIBs/SIBs) and are based on the inter- and deintercalation of K ions between two host materials.[1] The higher atomic weight and larger ionic radius of potassium ions results in lower gravimetric and volumetric capacities compared to LIBs.[2] But they offer similar advantages as SIBs (i.e. use of aluminium as current collector on both sides, evenly distributed potassium reserves) as well as graphite could be used as anode.[2,3] Also, they are expected to offer higher cell voltages due to the low standard potential of K/K+ vs. SHE of -2.93V.[3] To unlock the full potential of PIBs, cathode materials with high average potentials above 4 V need to be developed, which would significantly improve the energy density.[4] Polyanionic compounds, especially different Vanadium-Phosphates, are prepared and investigated for this purpose. Their thermal stability and diverse structural chemistry are advantageous for high energy PIBs. [2,5]

One of the often-used synthesis methods for polyanionic compounds is the solid-state reaction. [4] In my work this well-known synthesis was coupled with a spray-drying process and a subsequently sintering process for K3V2(PO4)3/C composites. This created spherical secondary particles with a size in the micrometer range and an open micro-porosity. (see attached image)
Through the addition of different amounts of organic sugars as a carbon source during the synthesis or sintering step an additional carbon coating of the primary and secondary particles was achieved, as well as the morphology of the secondary particles could be influenced. The influences of the different carbon contents during synthesis and sintering were investigated by thoroughly characterizing the morphology and crystal structure of the secondary particle with the help of SEM, BET, particle size distribution, XRD and porosity measurements. First electrochemical evaluation of the synthesized material was done by galvanostatic cycling the KVP/C composites against potassium.

References

[1] Min, X., et al., Energy Environ. Sci.,2021, 14, 2186
[2] Passerini, S., et al., Current Opinion in Electrochemistry, 2018, 9, 41-48
[3] Komaba, S. et al., Chem. Rec. 2019, 19, 735–745
[4] Komaba, S., et al., Chem. Rev. 2020, 120, 6358−6466
[5] Fan, L. et al., Small Methods 2021, 5, 2101131

Figure 1
Advanced Characterization Development for Metal Anodes in Aqueous Batteries
Authors: Catalina Sofia K. , Wang Jianbo , Chueh William C. , Mefford J. Tyler 
Published: February 2024

Renewable penetration of the electric grid necessitates inexpensive and safe energy storage solutions. With these priorities, aqueous batteries with metal anodes (Zn, Al, Mg, Sn, etc.) are an exciting area of development as they have low material costs, inherent safety, and high theoretical energy density. Understanding and quantifying the faradaic and chemical reactions occurring in aqueous alkaline batteries with metal anodes necessitates probing the solid, liquid, and gaseous phases that evolve during cycling. The interplay of plating, stripping, precipitation, disproportionation, and parasitic gases generation complicates our understanding of metal anode cycling behavior and often muddle the real failure mechanisms in aqueous batteries.
In our work, we have developed a robust toolbox of direct characterization tools to investigate metal anodes in aqueous batteries. Our investigation focuses on tin (Sn) as a largely unexplored metal anode and characterizes its performance and speciation during cycling. We will present a variety of methods to probe the charge/discharge speciation and efficiency losses to parasitic side reactions, including operando XRD, in-situ gas detection, RRDE, EQCM, and liquid 119Sn NMR. These techniques have allowed us to develop a mechanistic understanding of the Sn metal anode system and construct a high coulombic-efficiency, high utilization, and long cycle-life aqueous battery.
Zinc-Iron Rechargeable Flow Battery with High Energy Density
Authors: Fouladvari Negar , Gibertini Eugenio , Magagnin Luca 
Published: February 2024

In current research, electrochemical energy storage systems have gaining interest because they constitute an essential element in the development of sustainable energy technologies [1,2]. Among them, rechargeable flow batteries (RFBs) are one of the most promising technologies for the integration in grid-connected electricity, especially if combined with unpredictable and intermittent renewable energy sources, due to their high efficiency, power/energy independent sizing and room temperature operation [3]. At the moment, among all RFBs systems, the most investigated and advanced technology is the vanadium based RFB, characterized by an energy efficiency equal to 80% and energy density ranging 15-45 Wh/l [4]. However, nowadays the main bulk of research is focused on finding an economically convenient and technically competitive flow battery chemistry, able to ensure long lifetime and high energy efficiency [5,6]. In this study, a zinc-iron RFBs based on sulfate and sulfamate electrolytes will be presented, discussing the achievement of a charge density in the range 30-70 Wh/l. The combination of high energy efficiency of the Zn-Fe RFB with its ability to withstand a large number of charge/discharge cycles and the low cost, makes this battery system suitable for energy storage applications.

References

[1] Alotto, M. Guarnieri, and F. Moro. Renewable and Sustainable Energy Reviews 29 (2014): 325-335.
[2] Weber, M.M. Mench, J.P. Meyers, P.N. Ross, J.T. Gostick and Q. Liu. Journal of Applied Electrochemistry (2011), 41(10), 1137.
[3] Kear, A.A Shah, and F.C. Walsh. International journal of energy research, (2012), 36(11), 1105-1120.
[4] Ding, H. Zhang, X. Li, T. Liu, and F. Xing. The Journal of Physical Chemistry Letters, (2013), 4(8), 1281-1294.
[5] C- Xie, Y. Duan, W. Xu, H. Zhang, and X Li. Angewandte Chemie International Edition, (2017) 56 (47), 14953-14957.
[6] Selverston, R. F. Savinell, and J. S. Wainright. Journal of The Electrochemical Society 164, (2017): A1069-A1075.
Aqueous Electrochemical Degradation of Phosphate Framework Materials: Mechanisms and Mitigation Strategies
Authors: Vilciauskas Linas , Juodkazytė Jurga , Pilipavičius Jurgis , Petrulevičienė Milda , Tediashvili Davit 
Published: February 2024

Phosphate framework materials are attracting a lot of interest as very stable, structurally and electronically diverse materials, suitable for various electrochemical applications. For example, Na SuperIonic Conductor (NASICON) structure type AxMe2(PO4)3 (A = Li, Na, K; Me = Ti, V, Mn etc.) compounds, in addition to be being archetypical ionic conductors for solid state batteries are also potent electrode active materials for various devices such as aqueous batteries and Faradaic deionization cells. However, there is still a number of issues to be solved before their full potential could be utilized. This involves not only finding the right compositions of transition metals but also improving the stability of aqueous electrolyte/electrode interface. Aqueous stability and electrochemical degradation of electrode materials is related to complex acid-base equilibria, metal leaching, material dissolution, corrosion of cell components etc.
Some of the recent contributions in terms of understanding and enabling of Ti-, Mn- and V-based phosphate framework materials for the use in aqueous electrochemical systems is reviewed. The effects of parasitic reactions such as oxygen reduction (ORR) and hydrogen evolution (HER) and their relation to local pH changes towards the stability of NaTi2(PO4)3 (NTP) are determined. The results show that it is the local alkalinity which is responsible for most of the NTP degradation which is only accelerated at high currents. Several mitigation strategies by the use of conformal atomic layer deposited (ALD) coatings and oxygen management by the use of strongly reducing additives are suggested. The dissolution of transition metals as the main aqueous degradation mechanism for Na1+2xMnTi2-x(PO4)3 and Na3-xV2-xTix(PO4)3 positive electrodes is established. However, the results suggest that in Mn- and V-based positive aqueous battery electrodes it is not the material degradation which is responsible for most of the observed capacity fade per se but rather the loss of contact between particles and the conductive phase. The latter comes from the dissolution at the interfacial points but most of the electrode material, is shown to stay intact after extended cycling. Various metal substitution strategies leading to superior stability in half- and full-cells are presented.
[1] Plečkaitytė et al. J. Mater. Chem A, 9, 12670-12683 (2021).
[2] Snarskis et al. Chem. Mater., 33, 8394-8403 (2021).
[3] Tediashvili et al. Electrochim. Acta, 417, 140294 (2022).
[4] Petrulevičienė et al. Electrochim. Acta, 424, 140580 (2022).

Figure 1
Novel Electrode Designs and Configurations in Secondary Iron-Air Batteries
Authors: Kosin Marvin , Kassabeh Mohamad , Girschik Jan , Burfeind Jens , Grevé Anna 
Published: February 2024

Stationary energy storage solutions are urgently needed due to the challenges we face caused by the anthropogenic climate change. While Lithium-Ion batteries are still considered as state of the art within this field, the availability of lithium is limited.
The iron-air battery system is mainly superior due to the low criticality of the active materials. Iron is cheap and abundant, while air is supplied by the ambient atmosphere. During discharging oxygen from ambient air is reduced (oxygen reduction reaction, ORR) and evolved during charging (oxygen evolution reaction, OER). One of the main challenges towards stable metal-air batteries is the air-electrode. Those usually consist of a catalyst, a conductive additive, and – depending on the electrode design- of a binder. Carbon-based materials offer an excellent intrinsic activity towards the oxygen reduction and a high specific surface area. However, carbon corrodes in the potential range of the oxygen evolution reaction. Our work focuses on the development of novel electrode formulations for PTFE-bonded electrodes and novel self-supported electrode structures - based on galvanic deposition of nickel - and their implementation in iron-air batteries.
Within a first approach a mixed catalyst composed of MnO2 and NiO was investigated in a PTFE-bonded electrode with nickel as conductive additive. The electrode reached an initial activity of 0.77 V vs. RHE @ -25 mA cm-2 (ORR) and 1.57 V vs. RHE @ 25 mA cm-2 (OER) in 6 M KOH at room temperature. The potentials were stable for about 60 cycles (one cycle consisted of 60 min). MnO2 corrodes at OER potentials, which results in a decrease of activity. However, a partial substitution of MnO2 by NiO is beneficial for the cycling stability. In a second approach, a bifunctional nickel-cobalt-oxide based bifunctional catalyst was investigated within the same electrode system. An initial activity of 0.71 V vs. RHE and 1.63 V vs. RHE was observed for this system. Stable OER performance but a decrease ORR activity was observed within this system over time during cycling. To increase the cycling stability, dendritic nickel structures with a high intrinsic surface area were prepared with galvanic deposition. Our results indicate that the efficiency and stability of the battery can be improved by using this approach.

Figure 1
Exploring the Possibility of Aluminum Plating/Stripping from a Non-Corrosive Al(OTF)3-Based Electrolyte
Authors: Talari Mahla , Sarapulova Angelina , Zemlyanushin Eugen , Sabi Noha , Hofmann Andreas , Dsoke Sonia 
Published: February 2024

Aluminum abundance sources and the high theoretical volumetric capacity of Aluminum metal make Aluminum Batteries (ABs) promising energy storage systems[1]. Moreover, the low cost, sustainability, and low reactivity of Al in the air due to its passivation layer are advantageous in comparison to Li[2]. However, developing appropriate electrolytes for Aluminum batteries is a challenging topic that hinders their practical use[3]. Of particular concern is that the high charge density of the Al cation results in strong Coulombic interaction with the counter anions and solvents, which negatively impacts the solvation behavior of Al salts [4]. A non-corrosive ternary electrolyte, composed of Al(OTF)3/NMA/urea in the molar fraction of 0.05/0.76/0.19 respectively, was tested for Al battery system as an alternative to the common chloroaluminate-based electrolytes to enable Al plating/stripping[5]. Herein, several techniques, such as scanning electron microscope/energy-dispersive X-ray spectroscope (SEM/EDX), operando Optical microscopy examination, electrochemical quartz crystal (EQCM) and Gas chromatography (GC) were used to explore the Al electrodeposition from this electrolyte. Yet, the hydrogen evolution reaction was found to be associated with electrochemical activities observed in this multicomponent electrolyte rather than Al electrodeposition.

References

[1] Y. Zhang, S. Liu, Y. Ji, J. Ma, and H. Yu, “Emerging nonaqueous aluminum‐ion batteries: challenges, status, and perspectives,” Adv. Mater., vol. 30, no. 38, p. 1706310, 2018.
[2] S. K. Das, S. Mahapatra, and H. Lahan, “Aluminium-ion batteries: developments and challenges,” J. Mater. Chem. A, vol. 5, no. 14, pp. 6347–6367, 2017.
[3] J. Tu et al., “Nonaqueous rechargeable aluminum batteries: progresses, challenges, and perspectives,” Chem. Rev., vol. 121, no. 8, pp. 4903–4961, 2021.
[4] X. Han, Y. Bai, R. Zhao, Y. Li, F. Wu, and C. Wu, “Electrolytes for Rechargeable Aluminum Batteries,” Prog. Mater. Sci., p. 100960, 2022.
[5] T. Mandai and P. Johansson, “Al conductive haloaluminate-free non-aqueous room-temperature electrolytes,” J. Mater. Chem. A, vol. 3, no. 23, pp. 12230–12239, 2015.
Boosting the Stability and Performance of SOFCs: A New Approach to Oxygen Storage Capacity Using Lanthanum-Doped Ceria Interlayer Technology
Authors: Nguyen Xuan Dong , Lee Seok hee , Lim Hyung Tae , Shin Tae Ho 
Published: February 2024

Being carbon neutral is one of the world's most important objectives. More than 65 percent of the countries that emit harmful greenhouse gases have committed to achieving net-zero emissions by the middle of the century.[1] There are numerous essential ways to gather energy for worldwide missions, including fuel cells, solar power, wind power, etc. The growing marketplace of fuel cells is following the trend of green-energy demand. Solid oxide fuel cells (SOFCs) are gaining popularity in the next-generation energy industry due to their high energy conversion efficiency, fuel flexibility, and low emissions.[2]
The main challenges for the commercialization of SOCs that need to address are high performance, long-term durability, and effective cost. Stabilized zirconia such as Yttria-stabilized zirconia (YSZ) and Scandia-stabilized zirconia (ScSZ) is commonly used as a self-standing electrolyte support. The inability of zirconia-based electrolytes to react with Sr-rich cathode materials like LSC, LSCF, BSCF, etc. Therefore, the electrodes and the zirconia-based electrolyte must have the best-interlayered buffer structure. Optimizing interlayer microstructures to make them more effective at high-performance ESCs is of great interest. Several Rare-earth doped ceria (RDC) materials, including (Gd, Ce)O2, (Sm, Ce)O2, and (La, Ce)O2, have been used as efficient interlayers to lessen reactivity and preserve ionic conductivity in the interface. However, the difference in the thermal expansion coefficient (TEC) between the GDC and the YSZ poses a significant problem for starting and halting SOCs. In the present work, we focus on the commercial lanthanum-doped ceria (Ce0.6La0.4O1.8 - LDC) as a buffer layer between the YSZ electrolyte and the LSCF cathode because of its higher oxygen storage capacitance. The reactivity of the YSZ/GDC composite was higher than that of the YSZ/LDC composite. And the total conductivity of the LDC/YSZ composite is higher than GDC/YSZ composite even though LDC has lower conductivity than GDC. Moreover, the mismatching of TEC was reduced by replacing the GDC with the LDC bilayer.
Consequently, the maximum power density for the electrolyte-supported cell SOFC with LDC interlayer was ~0.55 W.cm−2 at 1073 K. A variety of additives (Co, Mn, and Cu) was added to the LDC buffer layer to examine the sintering properties. The addition of copper not only obtained the highest microstructural density but also improve mechanical stability under cost-effective processes.

References

[1] M. Meinshausen, N. Meinshausen, W. Hare, S.C. Raper, K. Frieler, R. Knutti, D.J. Frame, M.R.J.N. Allen, Greenhouse-gas emission targets for limiting global warming to 2 C, 458 (2009) 1158-1162.
[2] C. Graves, S.D. Ebbesen, S.H. Jensen, S.B. Simonsen, M.B.J.N.m. Mogensen, Eliminating degradation in solid oxide electrochemical cells by reversible operation, 14 (2015) 239-244.
Mixed Ionic-Electronic Conductivity in Oxygen-Free K2NiF4-Type Hydrides
Authors: Rodenburg Hendrik Pieter , Kyriakou Vasileios , Artrith Nongnuch , Ngene Peter 
Published: February 2024

Hydride-ion conductors and mixed hydride-electronic conductors are promising materials for numerous applications, for example as catalysts, catalyst supports or promoters for hydrogenation reactions, especially ammonia or methanol production. They could also be used in (electro)chemical energy conversion and storage devices such as batteries, fuel cells and reversible hydrogen storage systems. Therefore, there is a major interest in hydride-ion conductors with high conductivity at moderate temperatures.
Many presently known hydride-ion conductors are oxyhydrides, of which a large number have the K2NiF4-type structure.[1-5] As oxide ions occupy part of an oxyhydride’s anion sublattice, not all anions participate in hydride-ion transport, thereby potentially limiting the ionic conductivity at moderate temperatures. In this presentation, the synthesis and electrochemical characterization of several different oxygen-free K2NiF4-type structured hydride-ion conductors, such as Rb2CaH4 and Cs2CaH4, will be discussed.
By electrochemical analysis, the materials are found to exhibit mixed ionic-electronic conductivity at moderate temperatures. Small instabilities in the conductivity and TPD results which show that the materials release hydrogen gas indicate that the ionic conductivity is related to the presence of hydride-ion vacancies. In addition, computational results show that the measured activation energies are close to the expected values for hydride-ion transport.
The total conductivities at 200 °C are around 10-6 S cm-1, a significant portion of this being due to hydride-ion transport. The discovery of mixed hydride-electronic conductivity in these materials opens up new possibilities to explore mixed hydride-electronic conductors in catalysis and low-temperature energy conversion and storage applications.

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Figure: Illustration of one transport pathway that hydride-ions can take through K2NiF4-type structured materials. The path taken is informed by computational results.

Figure 1