bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stable Cycling of BiSbSe1.5Te1.5 Conversion-Alloying Anodes
Authors: Alvi Sajid Ali , Black Serra Ashley , Jozami Ignacio Samir , Akhtar Farid , Johansson Patrik 
Published: February 2024

Conversion-alloying anodes based on metal-selenides/tellurides have been explored extensively during the past decade for usage in lithium-ion batteries (LIBs), in order to increase cell energy density.1,2 Due to the large expansion and contraction during (de)lithiation, however, deterioration due to pulverization is a main hurdle to overcome for stable cycling. Strategies such as nano-structuring and composites have been applied to improve the mechanical stability, but no silver-bullet has yet been found.
Here we present proof-of-concept for a conversion-alloying based anode BiSbSe1.5Te1.5, a medium high-entropy alloy (MHEA). The main idea is that the increased entropy can enhance the mechanical properties via solid solution strengthening. The MHEA was synthesized using high-energy ball milling to get a single phase (R3m), which was subsequently used as the anode active material, and this without compositing with any carbon material, in contrast to previously reported Se/Te-based alloys.3,4 As a result, our half-cells (Li//MHEA) were able to attain stable cycling with high capacity (420 mAh g-1), agreeable capacity retention (84%), and coulombic efficiency (>99%) for 100 cycles at C/5 rate (Figure 1).5 The formation of a stable solid electrolyte interphase (SEI) was inferred by electrochemical impedance spectroscopy (EIS) data, showing reduced charge transfer resistance with cycling. Furthermore, operando XRD showed reversibility of the initial phases during (de)lithiation. We furthermore believe that moving from MHEAs to “proper” HEAs might further enhance the mechanical properties and stabilize the structure for even longer duration.
Figure 1: a) Charge-discharge curves and b) galvanostatic cycling of Li//BiSbSe1.5Te1.5.

References

Li, L., Zhao, J., Zhao, H. & Mao, J. Bi2Se0.5Te2.5/S, N-doped reduced graphene oxide as anode materials for high-performance lithium ion batteries. J. Alloys Compd.
920, 166003 (2022).

Fan, H. et al. Recent advances of metal telluride anodes for high-performance lithium/sodium-ion batteries. Mater. Horizons
9, 524–546 (2022).

Zhang, Z., Zhao, X. & Li, J. SnSe/carbon nanocomposite synthesized by high energy ball milling as an anode material for sodium-ion and lithium-ion batteries. Electrochim. Acta
176, 1296–1301 (2015).

Wei, Y. et al. Wrapping Sb2Te3 with a Graphite Layer toward High Volumetric Energy and Long Cycle Li-Ion Batteries. ACS Appl. Mater. Interfaces
12, 16264–16275 (2020).

Alvi, S. et al. To be submitted. (2023).

Figure 1
Electrochemical Synthesis of Molybdenum Ditelluride (MoTe2) and Its Potential Application as Negative Electrode Material for Sodium Ion Battery
Authors: Rajpura Kenil , Rajpura Kenil 
Published: February 2024

With the rapid expansion in energy demands and depletion of fossil fuel reservoirs, the importance of clean energy production and storage has increased drastically. The renewable energy recourses are cost effective, sustainable and carbon dioxide emission free alternatives. Nevertheless, this energy is not always available and needs to be stored. Lithium-ion batteries (LIBs) are rapidly used in various applications such as powering electronics, electric vehicles and grid energy storage. However, the source of lithium is extremely limited in earth crust, during mining it pollutes the environment and it is costly. Therefore, attention has been shifted towards development of sodium ion batteries (SIBs) which have wide reserves and low precursor cost and thus is considered as an appropriate choice for solar and wind energy development. The prime problem encountered in development of large-scale SIBs is the low effectiveness of appropriate anode material because of large size and sluggish kinetics of Na ions which limits the specific capacity as well as energy density.
Metal tellurides have emerged as a promising material for use as negative electrode in sodium-ion batteries due to its unique layered crystal structure, high intrinsic conductivity, and high trap density. Molybdenum ditelluride has more electric conductivity than selenides and sulfides. Other metals except molybdenum in the group takes part in alloying mechanism that leads to higher volume expansion and poor cycling stability.
In this study, we describe the synthesis of MoTe2 on copper and aluminium substrate by using predeposited molybdenum and electrodeposited tellurium at relatively low temperature of 450°C. Further we characterized the samples by X-Ray Diffraction, Raman Spectroscopy and Field Emission Scanning Electron Microscope for structural, elemental, and morphological properties, respectively. The synthesized material was used as negative electrode in sodium ion coin cell. The electrochemical performance of the coin cell will be correlated with the structural and electronic property of MoTe2.
Tin Nanoparticles As High-Performance Anode for Sodium-Based Batteries: Preparation and Operando XRD Investigation
Authors: Gammaitoni Giovanni , Bianchini Matteo 
Published: February 2024

Lithium-ion batteries (LIBs) have been dominating the energy storage market for decades, but the political and economic issues related to raw materials availability and cost is fueling the search for new electrochemical solutions. Sodium-based batteries (SBBs) are the most promising substitute to LIBs, because the similar physico-chemical properties of these two alkali guarantees the knowledge transfer from LIBs to SBBs and facilitate the working phenomena comprehension (so called rocking-chair mechanism).
The materials used as cathodes in LIBs often have a sodium-based analogue that offers acceptable performances in SBBs, yet this is not the case for anode materials. Graphite is the most used material as anode in LIBs and its electrochemical behaviour with lithium is based on the intercalation mechanism. Unfortunately, Na does not intercalate into graphite, pushing scientists to find other solutions, such as hard/soft carbons and alloying elements [1]. Tin, in particular, has a high theoretical capacity (847 mAh/g) due to the formation of the high-sodium-content alloy Na15Sn4, making it a promising candidate for the next generation of SBBs [2].
In our work tin nanoparticles and tin/carbon composites are prepared and analysed through electrochemical techniques. Being the sodiation of tin an alloying reaction, during the half cells discharge the increasing of sodium amount in tin is observed as the formation of high-sodium-content alloys according to the related phase diagram. We investigated the evolution of the system by operando XRD carried out at low current rate (coulometric titration), to confirm the expected phases based on the phase diagram are indeed observed. The results are corroborated by the electrochemical tests (galvanostatic cycling and voltammetry). Experimental data and theoretical information from literature are used to identify crystalline and amorphous phases [3]. The main issue linked to alloying materials is the high-volume expansion after discharge (420 % for tin), leading to fast capacity fade because of the solid electrolyte interphase (SEI) continuous destruction. For this reason, we prepared Sn/carbon composite structures able to mitigate the expansion and avoid the tin aggregation. In this way the capacity retention is improved, making this material a valid alternative for next generation batteries.
References
[1] Michael D. Slater, Donghan Kim, Eungje Lee, Christopher S. Johnson, Adv. Funct. Mater. 2013, 23, 947–958
[2] Shu-Min Zheng, Yan-Ru Tian, Ya-Xia Liu, Shuang Wang, Chao-Quan Hu, Bao Wang, Kai-Ming Wang, Rare Metals volume 40, pages272–289 (2021)
[3] Joshua M. Stratford, Martin Mayo, Phoebe K. Allan, Oliver Pecher, Olaf J. Borkiewicz,
Kamila M. Wiaderek, Karena W. Chapman, Chris J. Pickard, Andrew J. Morris,
and Clare P. Grey, J. Am. Chem. Soc. 2017, 139, 7273−7286
Electrocatalytic Activities of Sr2BO3Cl (B = Mn, Fe, Co, Ni) for Oxygen Reactions in Alkaline Solutions
Authors: Miyazaki Kohei , Ikeda Motohiro , Miyahara Yuto , Lee Changhee , Abe Takeshi 
Published: February 2024

The practical application of zinc-air rechargeable batteries, which are expected to be the next-generation rechargeable batteries, is challenged by the kinetically very slow oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Therefore, an air electrode catalyst with high activity for OER and ORR is required, and perovskite oxides have attracted attention as a candidate. To improve the catalytic activity of perovskite oxides, optimization of metal cations has been studied. On the other hand, anion substitution has also been reported to improve activity, and the oxychloride Sr2CoO3Cl with the Ruddlesden-Popper (RP) structure (composition: An+1BnO3n+1), which is a type of layered perovskite structure showed superior catalytic activities. However, there are still few studies on oxychlorides and the effect of anion substitution on the catalytic activity is still unknown. In this study, we compared the air electrode catalytic activity of RP-type acid chlorides Sr2
BO3Cl (B = Mn, Fe, Co, Ni) and LaSrBO4, an oxide with the same structure and valence, and investigated the B-site element dependence of the chloride ion substitution effect.
The ORR activity measurement results show that the oxychlorides with Co and Mn at the B site exhibited lower ORR overpotentials than the oxides, and that the ORR reaction electron number calculated from the Koutecký-Levich plots increases. Comparing the results for the same B-site elements, the oxychlorides had higher OER activity for all B-site elements. This suggests that chloride ion substitution may be effective in improving OER activity for all B-site elements, not only Co.
Supporting Critical Raw Material Circularity – Graphite from Waste LIBS to Zn-Air Batteries
Authors: Praats Reio , Liivand Kerli , Kruusenberg Ivar , Lundström Mari , Sainio Jani , Chernyaev Alexander 
Published: February 2024

The use of Li-ion batteries (LIBs) in electrical vehicles and consumer electronics is continuously on the rise which means that the amount of spent LIB (SLIB) is on the rise as well. The sustainable recycling of SLIB for production of secondary resources will prevent the loss of valuable materials and ensures safe and economical management of used batteries. During industrial black mass recycling process only Co and Ni from SLIBs is currently recycled, though LIBs contain many other valuable materials too. Graphite, which is used as an anode active material in LIBs, is discarded as a waste during industrial recycling process. Repurposing inexpensive waste graphite has a huge potential to be alternative for pristine graphite.
In this research a novel way to prepare bifunctional oxygen electrocatalyst from industrially produced and hydrometallurgically leached black mass leach residue is shown. The recycling leach residue is utilized as a valuable raw material, graphite and transition metal (Co, Mn, Ni) source, with N-precursor for the synthesis of N-Me-C graphite-based electrocatalyst. For the first time the battery metal residues, left into SLIBs recycling waste, are strategically exploited to achieve metal co-doping of graphite-based material. Battery derived electrocatalysts demonstrated promising electrocatalytic activity towards ORR and OER in alkaline media. Moreover, the novel bifunctional oxygen electrocatalysts were used in a rechargeable Zn-air battery as an air cathode catalyst and achieved a high-power density of 104 mW·cm-2 (Figure 1). The advantageous electrochemical activity of the catalyst materials was linked with its surface morphology, structure, porosity, and elemental composition.
This research shows the great potential of SLIBs black mass leach residue as a resource for the more sustainable production of high performance and low-cost bifunctional oxygen electrocatalyst appliable in Zn-air battery.

Figure 1
Revisiting Tin Oxide: A Systematic Investigation of Performance As a Function of Particle Size, Dopant and Electrolyte
Authors: Hakim Charifa , Aldroubi Soha , Andei Radu Dorin , Louvain Nicolas , Tolchard Julian Richard 
Published: February 2024

The reliable application of conversion and alloying materials as high capacity electrodes in Li-ion batteries has been a mostly elusive ambition for nearly 30 years. The most notable successes being the commercialisation of the Tin based Nexelion™ chemistry by Sony in 2005, and the current commercialisation of Si and SiOx materials as anode additives today. Despite the relatively narrow scope of commercialised systems however, the scientific literature remains vibrant on this topic, spurred on by the allure of specific capacities in excess of 1000mAh/g.
The limitations of conversion systems are well known: Extremely poor first cycle efficiencies, large voltage hysteresis, wide voltage windows and generally poor cyclability arising from the massive morphological changes during cycling. Nanostructuring is widely regarded as the best route to mitigating these problems, and the literature is accordingly rich with complex and “photogenic” nanostructures and composites demonstrating greatly improved performance. These are however often produced by routes which are difficult to scale.
Within the SMICE-Li project we have been revisiting conversion and conversion-alloy materials with an inherently scalable synthesis route: Flame Spray Pyrolysis. This involves the continuous combustion of an atomised spray of combustible precursors and yields an inherently nanoscaled product which can be controllably grown and modified with post-synthesis thermal annealing.
We will present the results of a systematic study into doped SnO2 as a function of dopant, particle size, cycling voltage window and electrolyte formulation. Clear differences in cyclability are observed for SnO2 just by altering particle size from ~7nm to ~25nm, but these may be suppressed by the addition of dopants. Clear performance differences between dopants (Ni, Fe, Co, Mn; Ti) are also found, with results replicated across a range of organic-carbonate and ionic liquid electrolyte compositions. For all compositions the Sn-SnO2 Conversion reaction is seen to be the major source of capacity fade, but some dopants stabilise the Sn-LixSn alloy reaction whilst others do not. Restricting the voltage cycling window to limit cycling to only the alloy reaction greatly improves cyclabilty in all compositions, and for the best performing compositions, stable cycling with capacity retention in excess of 450mAh/g is achieved after 300 cycles.
Insights into the Development and Performances of Ionogel-Based Electrolytes for Solid-State Lithium-Based Batteries
Authors: Zhang Ying , Gerbaldi Claudio , Elia Giuseppe Antonio 
Published: February 2024

Solid-state electrolytes (SSEs) aim to overcome safety issues, decrease package volume, and increase the energy density of next-generation energy storage devices, such as Li-ion and post-lithium batteries. Among different types of SSEs, the ionogel (or ion gel) systems, in which polymer electrolytes are doped with room-temperature ionic liquids (RTILs), are amongst the most attractive choices to reach ionic conductivity values comparable to those of liquid electrolytes, ensuring better safety and electrode/electrolyte interface stability [1]. In our previous studies, several ionogel samples were prepared by in-situ UV-curing [2]. Here, we present the results of newly optimized methacrylate-based solid-state electrolyte systems conceived for ambient temperature cycling with high-energy cathodes. We characterized the electrolyte formulations using various physico-chemical and electrochemical methods, including gel content, FTIR, rheology, DMTA, TGA, SEM, voltammetry, impedance spectroscopy, and galvanostatic cycling. The focus is particularly on the influence of using two different RTILs as reaction media on the properties of the resulting materials and their electrochemical behaviours. The achieved results indicate that viscosity affects the polymerization kinetics of the ionogels, which in turn affects their thermal stability and galvanostatic cycling behavior. The obtained ready-to-use and self-standing crosslinked ionogel electrolyte membranes (~100 µm thickness) showed relatively high ionic conductivity (0.8 to 2 mS/cm at 20 °C) and anodic stability (up to 4.5-5 V vs. Li). Lithium lab-scale cells were assembled with ionogel-polymerized-on-NMC-cathodes for galvanostatic cycling measurements, and they demonstrated initial discharge capacities of around 180 mAh/g at low C-rate in the voltage range of 3.0-4.3 V at room temperature. Furthermore, motivated by the demand of increasing the overall performance of the SSEs, different types of composite solid electrolytes are now under our investigation and further development, including the utilization of active and inert inorganic fillers. For example, we introduced LLZO ceramic microparticles into the aforementioned ionogel systems for fabricating composite SSEs via in-situ photopolymerization. So far, the best achieved preliminary cycling results show enhanced and more stable cycling behaviour at higher C-rates up to 0.2C at room temperature, suggesting the promising prospects of our composite SSEs and their potential contribution to the fabrication of solid-state, high-energy lithium-based batteries.
Acknowledgements: This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 860403.
References:
[1] Schnell J. et al. J. Power Sources
2018, 382, 160.
[2] Gerbaldi C. et al. Journal of Power Sources
2010, 195, 1706.

Figure 1
First-Principles Calculations of Fluoride-Ion Migration in Fluorine-Ion Battery Electrolyte Material K2BiF5
Authors: Moriwake Hiroki , Kuwabara Akihide , Ogawa Takafumi , Fisher Craig , Ikuhara Yuichi , Niwa Eiki , Hamaguchi Kaisei , Mori Daisuke 
Published: February 2024

Fluoride-Ion migration in K2BiF5 was studied using first-principles static and dynamic calculations. Due to presence of edge sharing BiF7 chain along b axis in this structure, one dimensional Fluoride-Ion migrations alongBiF7 chain strongly suggested. Our calculation revealed not only this Fluoride-Ion migrations along BiF7 chain, but also F ion migrations between BiF7 chain were observed. First-principles calculations of the electronic density of states indicate that K2BiF5 has a large band gap of about 4.8 eV, making it suitable as an ionic conductor. The Fluoride-Ion conduction in the b-axis direction was strongly suggested by the presence of BiF7 chains sharing a ridge in the b-axis direction in the structure of this material, but the F-ion conduction path analysis by first-principles molecular dynamics shown in Fig. 1 indicates that the F-ions are not only in the b-axis direction and in BiF7 chains, but are also active betweenBiF7 The active Fluoride-Ion are determined by the elastic band method. The activation energy determined by the elastic band method is 0.19 eV within a BiF7 chain, whereas it is 0.25 eV between BiF7 chains, indicating that F ions can conduct with the same activation energy as within a BiF7 chain.
Acknowledgments
This work was supported by the RISING3 (JPNP21006) projects from the New Energy and Industrial Technology Development Organization (NEDO), Japan.

Figure 1
Lithium Silicates as an Artificial SEI for Rechargeable Lithium Metal Batteries
Authors: Chen Yue-Sheng , Su Yu-Sheng 
Published: February 2024

The major motivation of replacing lithium-ion batteries with lithium metal batteries is to obtain higher energy density by adopting the metallic lithium anode (3860 mAh g-1, theoretically), which means they can store more energy in the same volume or weight. One of the main challenges of rechargeable lithium metal batteries is the formation of lithium dendrites during the charging process.1 Lithium dendrites are tiny needle-like structures that can grow from the surface of the lithium metal electrode and penetrate the separator, causing battery short-circuiting. This can lead to safety issues, including the potential for fire or explosion. Another challenge is the formation of solid-electrolyte interface (SEI) on the surface of the lithium metal electrode, which can reduce the battery's efficiency and cycle life.2 The SEI layer can also lead to the formation of inactive lithium and increase the risk of dendrite growth.
In the present work, various lithium silicates have been synthesized to be implemented as the artificial SEI layer via a facile dry coating method.3,4 The lithium silicate coating acts as a protective barrier that prevents direct contact between the lithium metal and the electrolyte, which may cause undesirable side reactions and reduce the efficiency and lifespan of the battery.4 The lithium silicate-based artificial SEI layer improves the stability and efficiency of lithium metal batteries by reducing unwanted surface reactions, improving ion transport kinetics, and protecting the lithium metal anode from mechanical deformation and unstable SEI formation during extended cycling. This laminated lithium anode structure could be an effective design for the future development of long-cycle-life lithium metal batteries.

F. Wu et al., Energy Storage Materials, 15, 148–170 (2018).

X.-B. Cheng et al., Adv. Sci., 3, 1500213 (2016).

A. Bhat, P. Sireesha, Y. Chen, and Y. Su, ChemElectroChem, 9 (2022) https://onlinelibrary.wiley.com/doi/10.1002/celc.202200772.

Y.-S. Su, K.-C. Hsiao, P. Sireesha, and J.-Y. Huang, Batteries, 8, 2 (2022).

Figure 1
Low-Cost and Sustainable Aqueous Lithium-Ion Batteries by All-Organic PTCDI Anodes
Authors: Karlsmo Martin , Brown John , Grimaud Alexis , Johansson Patrik 
Published: February 2024

Electrolyte engineering has been key to the advancement of aqueous lithium-ion batteries (ALIBs), for example, the introduction of water-in-salt electrolytes (WiSEs) has enabled ALIBs to cycle well and to operate at potentials far beyond the electrochemical stability window of water. WiSEs are, however, intrinsically based on high concentrations of salt(s) which furthermore often are expensive and fluorinated, and therefore defeats the aim of ALIBs being low-cost and sustainable. Strategies to circumvent this issue have been to add co-solvents and/or diluents to decrease the overall electrolyte concentration or customize the anion and salt concentration to each battery chemistry. The clean and green ethos of ALIBs can be enhanced by using organic active materials (AMs), but these are unfortunately often water soluble and therefore requires an electrolyte designed to mitigate dissolution/electrode de-attachment.
Herein, we for the first time implement perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) as the anode AM for ALIBs. We demonstrate that by appropriate aqueous electrolyte selection we can truly mitigate electrode de-attachment, leading to excellent properties in terms of capacity, rate capability, cycling stability, and Coulombic efficiency. All things considered, this endeavour intends to further reduce the kWh/€ and thereby reinforcing the feasibility of more cost-effective large-scale battery energy storage solutions

Fig 1. Long term galvanostatic cycling of an all-organic PTCDI electrode in a PTCDI/low conc. aqueous el./LFP cell set-up. Inset shows the chemical structure of PTCDI and the corresponding charge/discharge voltage curves.

Figure 1