bluuebunny/crossref_metadata_2025_split huggingface dataset:
Interfacial Chemical Stability of Doped Li7-XLa3Zr2
-X(Nb/TaX)O12 with LiCoO2 Electrode Material
Authors: Pateli Ioanna Maria , Vestli Mihkel , Irvine John 
Published: February 2024

Garnet-type oxide solid state electrolytes (SEs) are promising candidates due to their potential high ionic conductivity and chemical stability with Li for the replacement of flammable liquid electrolytes used in the current Li-ion batteries. Intense research has been focused on optimising the interface of garnets with Li, with the positive side to be somehow neglected. A significant issue of oxide SEs, hurdling their industrial application, is their poor contact with positive materials due to their rigidity. Poor interfacial contact leads to the need of co-sintering at high temperatures (> 400 °C), which enables side reactions and unwanted processes like cation intermixing, diffusion of elements and formation of non-conductive secondary mixed phases.
In this work the chemical stability of Ta and Nb doped LLZO garnet SE was tested in contact with LiCoO2, a common positive material used in the battery industry. Initially, mixed powders of SE and active material were heat treated and studied using Raman spectroscopy and scanning electron microscopy to observe side reactions. In order to improve contact between the two materials, instead of already synthesized crystalline powder, nitrate precursors were also used for in-situ synthesis of LiCoO2 material in contact with the garnet. Mixtures of the SE powder and nitrate precursors for LiCoO2 were also heat-treated at various temperatures for different time periods in different gas atmospheres. The heat-treated materials were then analysed extensively using scanning electron microscopy coupled with energy dispersive X-Ray element mapping and with Raman microscopy to prove the existence or absence of secondary mixed phases at given conditions. Additionally, the optimized heat-treatment conditions were adapted for layered garnet SE/LiCoO2 samples to study the actual electrolyte/electrode interface at the same conditions used for powder mixtures. Based on the results the symmetrical LiCoO2/garnet SE/LiCoO2 cells will be prepared and tested electrochemically.
The Mg Electrode Cycling Mechanism in Simple Salt Glyme Electrolytes
Authors: Sankowski Andrzej , Dimogiannis Konstantinios , Holc Conrad , Parmenter Christopher , Newton Graham , Walsh Darren , O'Shea James , Khlobystov Andrei , Johnson Lee 
Published: February 2024

The lithium-ion battery (LIB) has been at the forefront of innovations in energy storage since its commercialisation over 30 years ago. As we reach the practical specific capacity limit of current state-of-the-art materials, novel and innovative battery technologies are required to satiate the requirements of energy intensive applications such as electric vehicles.
1
The use of a lithium metal negative electrode has been proposed to increase the energy density, however the high reactivity causes poor cycling performance due to electrolyte degradation, dendrite formation and safety issues.
2
The magnesium electrode offers a solution that has double the theoretical volumetric capacity of the lithium electrode while simultaneously mitigating dendritic growth, reducing raw material costs and greatly increasing sustainability.
3,4
Previous work has shown that traditional LIB electrolytes are not compatible with magnesium metal, and the plating and stripping mechanism that underpins how magnesium electrodes cycle is poorly understood.
5

Here we explored the mechanism of magnesium plating and stripping in glyme-based electrolytes with a range of additional additives. We show that in the pure electrolyte solution, interphase formation is critical to stable cycling but that this is accompanied by significant degradation and accumulation of inactive Mg.6 We establish the three-dimensional chemical composition of Mg deposits in the different electrolyte formulations using a combination of focused ion beam-scanning electron microscopy (FIB-SEM), energy dispersive x-ray spectroscopy (EDX) and transmission electron microscopy (TEM). We use these findings to develop a mechanistic understanding that explains the electrochemical cycling performance of magnesium metal negative electrodes. In situ electrochemical quartz crystal microbalance (EQCM) measurements are used to evaluate the plating and stripping efficiency of the electrodes and to identify non-electrochemical degradation reactions between Mg and the electrolyte solutions.
References:
1 R. Shah, V. Mittal, E. Matsil and A. Rosenkranz, Adv. Mech. Eng., 2021, 13, 1–9.
2 Z. Hu, J. Li, X. Zhang and Y. Zhu, Front. Chem., 2020, 8, 409.
3 M. Fichtner, Magnesium Batteries: Research and Applications, Royal Society of Chemistry, 2019, vol. 2020.
4 R. Attias, M. Salama, B. Hirsch, Y. Goffer and D. Aurbach, Joule, 2019, 3, 27–52.
5 S. B. Son, T. Gao, S. P. Harvey, K. X. Steirer, A. Stokes, A. Norman, C. Wang, A. Cresce, K. Xu and C. Ban, Nat. Chem., 2018, 10, 532–539.
6 C. Holc, K. Dimogiannis, E. Hopkinson and L. R. Johnson, ACS Appl. Mater. Interfaces, 2021, 13, 29708–29713.
Highly Concentrated Electrolytes for Lithium Sulfur Batteries – the Role of the Anion(s)
Authors: Kottarathil Aginmariya , Marczewski Maciej , Johansson Patrik , Wieczorek Wladyslaw 
Published: February 2024

Lithium-sulfur batteries (Li-S) have attracted a lot of attention as a alternative/complement to lithium-ion batteries (LIBs) – due to both high energy density, availability, and inexpensive materials used.[1]
Yet, dissolution of sulfur from the C/S cathode and subsequent shuttling of lithium polysulfides (LiPS) to the anode as well as the instability of the Li metal anode itself are true scientific and technological challenges. Advancing in the field of electrolytes is one promising way to overcome both issues.
Switching from the standard 1 M electrolyte design of LIBs to highly concentrated electrolytes (HCEs) may both prevent the dissolution of LiPSs and hinder dendrite formation at the lithium metal anode.[2]
Here we combine experimental methods and computational approaches to investigate several HCEs based on various Li-salts in several standard organic solvents. Experimentally we targeted electrochemical properties, local electrolyte structure, and physico-chemical properties, with focus on the role(s) of the Li-salt anions. Furthermore, to predict the solubility of sulfur the conductor like screening model for real solvents (COSMO-RS), a computational fluid phase thermodynamic approach, was used.[3] Overall, the challenges and opportunities associated with the use of HCEs in Li-S batteries will be addressed, also highlighting potential areas for future research and development.
References

Peng et al., "Drastic effect of salt concentration in ionic liquid on performance of lithium sulfur battery." Journal of the Electrochemical Society 169.5 (2022): 050515.

Suo et al., "A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries." Nature communications 4.1 (2013): 1481.

Jeschke and P. Johansson, "Predicting the Solubility of Sulfur: A COSMO‐RS‐Based Approach to Investigate Electrolytes for Li–S Batteries." Chemistry–A European Journal 23.38 (2017): 9130-9136.
A New Approach in Surface Modification of Manganese Based Cathode Materials for Enhanced Performance in Zinc Aqueous Batteries
Authors: Zhanadilov Orynbay , Kim Hee Jae , Myung Seung-Taek 
Published: February 2024

With the growing demand for sustainable and environmentally friendly energy storage solutions, zinc-aqueous batteries have emerged as promising alternatives to conventional lithium-ion batteries. Among the various cathode materials studied for zinc-aqueous batteries, manganese dioxide (MnO2) has garnered significant attention due to its high theoretical capacity, abundance, and non-toxic nature. However, the intrinsic limitations of MnO2, including low electrical conductivity and sluggish kinetics, have hindered its practical application. To address the aforementioned limitations, we present a new approach in surface modification of KxMnO2 cathode with improved electrochemical performance for zinc-aqueous batteries.
In this study, the KxMnO2 cathode material’s surface has been fluorinated, that enhances capacity retention of the material and effectively improves the overall electrochemical performance. Structural and morphological characterizations of the surface modified KxMnO2 were performed using operando X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), X-ray Absorption Near Edge Spectroscopy (XANES) and thermogravimetric analysis (TGA). Furthermore, X-ray photoelectron spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) confirmed the successful fluorination of the material surface.
Electrochemical tests, including cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS), were conducted to evaluate the performance of the surface fluorinated KxMnO2 cathode in comparison to pristine KxMnO2. The results demonstrated a remarkable improvement in the specific capacity, rate capability, and cycling stability of the modified cathode. The improvement of electrochemical performance can be attributed to the effect of the fluorine element, which alleviates the structural degradation of KxMnO2 during cycling. The improved electrochemical performance of the KxMnO2 cathode paves the way for the development of high-performance, cost-effective, and environmentally friendly zinc-aqueous batteries.
Highly Concentration Aqueous Electrolytes for Zinc Metal Batteries
Authors: Al Kathemi Ibrahim , Antonietti Markus , Bouchal Roza 
Published: February 2024

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

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

References

[1] J. Yang, B. Yin, Y. Sun, H. Pan, W. Sun, B. Jia, S. Zhang, T. Ma, Nano-Micro Lett.
2022, 14, 1–47.
[2] Y. Shi, Y. Chen, L. Shi, K. Wang, B. Wang, L. Li, Y. Ma, Y. Li, Z. Sun, W. Ali, S. Ding, Small
2020, 16.
[3] D. Kundu, B. D. Adams, V. Duffort, S. H. Vajargah, L. F. Nazar, Nat. Energy
2016, 1, 1–8.
[4] H. Qin, W. Kuang, D. Huang, X. Zhang, J. Liu, L. Yi, F. Shen, Z. Wei, Y. Huang, J. Xu, H. He, J. Mater. Chem. A
2022, 10, 17440–17451.
[5] F. Wang, O. Borodin, T. Gao, X. Fan, W. Sun, F. Han, A. Faraone, J. A. Dura, K. Xu, C. Wang, Nat.
Mater.
2018, 17, 543–549.
Artificial SEI Layer Combined with Single-Ion Polymer Electrolytes to Prevent Dendrite Growth in Lithium Metal Batteries
Authors: Wan Jiajia , Liu Xu , Passerini Stefano , Paillard Elie 
Published: February 2024

Li-metal batteries have the potential to become the next generation of batteries since they can provide an increased energy density vs. Li-ion batteries. However, the safety issue caused by the inhomogeneous Li deposition and Li dendrite growth greatly limits their commercial application. Several methods have been proposed to address this issue. On the one hand, when Li ions are released from one electrode and consumed at the other electrode, it causes a salt concentration gradient. Besides, the electrical migration of anions in the opposite direction aggravates the concentration of gradient since anions do not react at the electrodes. Fast dendritic growth then occurs when the current is high enough to fully deplete the Li+ ion at the anode during charge. Thus, suppressing concentration gradient by immobilizing the anions would in principle solve the fast dendritic growth issue. On the other hand, the Solid Electrolyte Interphase (SEI) plays a crucial role in the operation of Li metal batteries since it prevents further reduction and continuous electrolyte reaction. SEI derives from the passivation layer formed onto the surface of Li metal under dry air during lithium foil extrusion and then evolves further in contact with the electrolytes and during subsequent electrochemical Li stripping/plating. The SEI is inhomogeneous and since it contains lower resistance pathways for Li+ transport, it favors inhomogeneous deposition at any current. Thus, SEI engineering, in order to favor the homogeneity of current density and enhanced mechanical properties to confine lithium could, in principle, improve the performance of Li metal batteries.
Thus, we studied the use of single-ion conducting polymers with high cationic transference numbers (tLi+ close to 1) as artificial SEIs (art-SEIs) since they include immobile anions and thus prevent Li+ depletion during charge and, at the same time, improve lithium metal confinement and the homogeneity of current density. Our results show much improved homogeneity of Li deposition and cycling stability after single-ion art-SEI coating using an ether-based liquid electrolyte combined with a separator. Nevertheless, it could not enable long-term cycling as the separator does not enable homogeneous pressure and current density onto the lithium anode. Thus, the use of a single-ion conducting solid polymer electrolyte was combined with a single-ion conducting art-SEI (as illustrated in Figure 1). This strategy allows the suppression of salt concentration gradients, inhomogeneous pressure and current density, thus enables homogeneous Li deposition and long-term cycling of Li metal anode.

Figure 1
Revealing the Cycling and Degradation Mechanism of Bi-Metallates As Anode Materials for Na-Ion Batteries
Authors: Brennhagen Anders , Skautvedt Casper , Cavallo Carmen , Skurtveit Amalie , Wragg David Stephen , Koposov Alexey , Sjåstad Anja Olafsen , Vajeeston Ponniah , Fjellvåg Helmer 
Published: February 2024

Na-ion batteries (NIBs) represent an emerging alternative to modern Li-ion batteries. To improve the overall performance of NIBs it is crucial to develop new types of anode materials with high capacity and long cycle life. Among the anode candidates, materials operating under combined conversion and alloying mechanisms (CAMs) are considered as promising. They are capable of delivering high capacity, however, despite theoretical predictions the cycling stability is still below expectations. Therefore, a comprehensive understanding of the cycling and degradation mechanisms of CAMs is crucial to improve their performance. However, these materials undergo multiple chemical transformations, which often involves formation of amorphous and nanocrystalline phases during cycling. Such chemical complexity substantially impedes their full characterization and understanding.
Bismuth metallates, with a general formula of Bi-TM-O (TM = transition metal), is a group of ternary CAMs. Their general cycling mechanism consists of an irreversible conversion reaction, which leads to formation of Bi nanoparticles embedded in a Na-TM-O matrix during the first sodiation. This is followed by a reversible two-step alloying reaction leading to formation of Na3Bi with NaBi as an intermediate phase. In this work, we have used operando X-ray diffraction over the course of ∼30 cycles to study the cycling and degradation mechanisms of two CAMs - Bi2MoO6 and BiFeO3. With the help of ex situ X-ray absorption spectroscopy and pair distribution function (PDF) analysis, we have revealed new insights into these materials in addition to confirming the general cycling mechanism.
Both materials form the cubic phase of Na3Bi (c-Na3Bi) in the sodiated state with some noticeable differences. While, the hexagonal Na3Bi (h-Na3Bi) phase starts to form after 10 cycles in Bi2MoO6, a combination of c-Na3Bi and h-Na3Bi can be observed after the first cycle in BiFeO3. The formation of c-Na3Bi is kinetically favorable in these systems, while h-Na3Bi is the more thermodynamically stable and, therefore, forms later in the cycling process. Both materials shows three distinct regions of capacity degradation, where the first is initiated by a growth in the crystallite sizes of Bi-particles. This is followed by a disappearance of the Bi-phase as the second step. The last degradation phase is related to the disappearance of the NaBi-phase and locking the system in the sodiated state. The present talk will discuss the mechanisms of these degradation steps in view of the future development of CAMs in greater details.

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

With high theoretical capacities (820 mAh g−1 and 5855 mAh cm−3), suitable electrochemical potential (−0.763 V vs standard hydrogen electrode), low cost, and rich abundance of component materials, aqueous zinc-ion batteries (ZIBs) and capacitors (ZICs) have exhibited great promise for grid-level energy storage and other stationary applications. Zn metal as excessive Zn are often used to compensate for the uncontrollable dendritic growth, corrosion behaviour, and low Coulombic efficiency (CE) of the Zn metal. As such, most of the ZIBs and ZICs developed using these electrode materials exhibited actual device energy and power densities that were significantly lower than the corresponding theoretical values. Another key performance metric that needs to be improved in ZIBs is their high-rate charge and discharge. In addition to the dendrite-derived problems commonly experienced in batteries based on other metal anodes, ZIBs are disadvantaged by hydrogen gas evolution from water decomposition especially under high-rate charge/discharge, leading to poor cycle life.
Herein, an ultrafast, stable, and high-loading polymer anode for aqueous Zn-ion batteries and capacitors (ZIBs and ZICs) is developed by engineering both the electrode and electrolyte. The anode polymer is rationally prepared to have a suitable electronic structure and a large π-conjugated structure, whereas the electrolyte is manufactured based on the superiority of trif late anions over sulfate anions, as analyzed and confirmed via experiments and simulations. This dual engineering results in an optimal polymer anode with a low discharge potential, near-theoretical capacity, ultrahigh-loading capability (≈50 mg cm−2), ultrafast rate (100 A g−1), and ultralong lifespan (one million cycles). Its mechanism involves reversible Zn2+/proton co-storage at the carbonyl site. When the polymer anode is coupled with cathodes for both ZIB and ZIC applications, the devices demonstrate ultrahigh power densities and ultralong lifespans, far surpassing those of corresponding Zn-metal-based devices.

Figure 1
Influence of Salt Concentration on Electrochemical Stability Window in Aqueous Electrolytes
Authors: Wahab Abdul , Pfeifer Rene , Zafar Zahid Ali , Cervenka Jiri 
Published: February 2024

The thermodynamic limit of water electrolysis restricts the output voltage of aqueous metal ion batteries (MIBs) due to the low electrochemical stability window of water (1.23 V) in dilute electrolytes. It occurs due to the electrolysis of free water molecules into O2 or H2. Such value is unfortunately too low for many applications. For effective utilization of this technology, the ESW needs to be expanded to at least 2 V to achieve high energy density in metal batteries. Interestingly, water electrolysis can be suppressed by binding free water content with high concentrations of salts in highly concentrated water-in-salt electrolytes.
In this work, low-cost non-flammable aqueous Zn(ClO4)2 electrolytes have been studied for their electrochemical behaviour at different concentrations. The electrolytes have been evaluated via Raman spectroscopic analysis to examine the modification in local water structures associated with increasing salt concentration. We also used linear sweep voltammetry on a glassy carbon electrode to determine the electrochemical stability window of the electrolytes. Electrochemical results indicate the existence of two distinct regions in the concentration behavior of the onset potential for oxygen evolution reaction (OER) at a cut-off current density of 0.1 mA cm-2. In dilute electrolytes, the overpotential in OER increases with a low slope with increasing concentration, while there is a sharper overpotential increase at higher salt concentrations in the water-in-salt electrolytes. Raman spectroscopic analysis provides evidence of this electrochemical stability expansion as being a result of the disruption of the hydrogen bonding network present in pure water. A more compact and strongly coordinated ion hydration structure occurs in the water-in-salt electrolytes. In this way, a significant increase in oxidative stability and a decline in the Zn oxidation overpotential has been achieved in the highly concentrated water-in-salt electrolytes. Our results indicate that the Zn(ClO4)2 water-in-salt electrolytes offer more efficient Zn redox reactions and a higher electrochemical stability window than the diluted aqueous electrolytes, which is particularly beneficial for the development of high-voltage aqueous Zn ion batteries [1].

References

[1] Z. A. Zafar, G. Abbas, K. Knížek, M. Šilhavík, P. Kumar, P. Jiříček, J. Houdková, O. Frank, J. Červenka, J. Mater. Chem. A
10 (2022) 2064-2074.