bluuebunny/crossref_metadata_2025 huggingface dataset:
Powering Smart Windows: Unveiling Crystal Structure and Al-Ion Storage Correlation in WO3 Electrode Via XRD for Aqueous Al-Ion Battery with Real-Time Energy-Level Indication
Authors: Roy Rahuldeb , Ganesha Mukhesh K , Dutta Pritha , Singh Ashutosh Kumar
Published: February 2024

The potential for using aqueous-based electrochromic batteries in colour indicator energy storage devices, particularly energy-efficient buildings and wearable technology with visible energy level performance, is significant. Unfortunately, many materials that are able to change colour upon ion intercalation have low optical contrast and capacity. To address this, multivalent ions can be utilized, providing multiple electrons and thus increasing optical contrast and capacity. This work presents a novel Al-ion electrochromic battery with WO3 as the cathode material, Al metal as the anode and AlCl3 as the aqueous electrolyte. X-ray diffraction results demonstrate the high structural stability of the optimized WO3 film (~170 nm), which only experienced a 0.69 pm change during Al-ion intercalation and de-intercalation. A DC-EES device with two cathodes on either side of an Al metal film anode exhibited superior performance, with an open circuit potential of 1.2 V and a capacity of 200 mAh/m2 at 0.5 A/m2. Additionally, the device displayed excellent electrochromic behaviour upon discharge, achieving an optical contrast of ~70%. These results illustrate the promising potential of Al-ion electrochromic batteries as a cost-effective and safe option for applications such as smart windows and energy storage displays in modern infrastructures.

Figure 1
Rationally Designed Spherical V2O5 Encapsulated by 2d-VS2 as High Capacity Insertion Cathode for Mg-Ion Battery
Authors: Mukherjee Ayan , Chakrabarty Sankalpita , Noked Malachi
Published: February 2024

Owing to high energy density and economic viability, rechargeable Mg-ion batteries (MIB) are considered as alternative to lithium-ion batteries. However, beside chevrel phase, none of conventional inorganic cathode materials demonstrate reversible intercalation/deintercalation of Mg+2 ions in anhydrous electrolyte system. The lack of high voltage and high-capacity cathode frustrates the realization of MIB. Previous studies indicated that vanadium pentoxide (V2O5) has potential to reversibly insert\extract Mg ions. However, many attempts to utilize V2O5 demonstrated limited electrochemical response, due to hindered Mg ion mobility in solid. Herein, we demonstrated a tailored approach to synthesize uniformly dispersed spherical V2O5 homogeneously coated with 2D VS2 through a facile in-situ chemical method and study the electrochemical activity in 0.2 M Mg(TFSI)2 + MgCl2 in DME electrolyte system and Mg metal anode. The V2O5@VS2 cathode exhibit the highest reported 1st discharge capacity of ~ 260 mA.h.g-1, excellent stability, retention and restricted capacity fading after 100 cycles which witness the prominence of VS2 coating in rationally designed V2O5 as a cathode material in non-aqueous electrolyte system for next generation high capacity MIB. Most interestingly, exact phase and morphology is completely retained even after repeated Mg+2 ion intercalation/deintercalation at different current rates, demonstrating pronounced electrochemical activity in anhydrous magnesium electrolyte and realization of a practical MIB.
Exploring Battery Materials for Ca Batteries
Authors: Zhao-Karger Zhirong , Fichtner Maximilian
Published: February 2024

Rechargeable calcium (Ca) batteries have the prospects of high energy, low-cost and sustainability. Ca metal has a low reduction potential of -2.9 V vs. NHE (close to that of lithium -3.0 V)) and a high capacity, and thus the voltage and energy density of Ca batteries is potentially comparable with lithium-ion batteries. However, divalent Ca-ions and reactive Ca metal strongly interact with cathode materials and electrolyte solutions, leading to high charge-transfer barriers at the electrode-electrolyte interfaces and consequently low electrochemical performance. Herein, we will present the recent progress in the development of stable calcium tetrakis(hexafluoroisopropyloxy) borate Ca[B(hfip)4]2 (hfip = CH(CF3)2) electrolytes and the search for suitable cathode materials. We will discuss the interfacial properties of Ca anodes in liquid electrolytes and the chemistry of sulfur conversion electrodes in Ca batteries.

References

Li, O. Fuhr, M. Fichtner, Z. Zhao-Karger, Towards stable and efficient electrolytes for room-temperature rechargeable calcium batteries.Energy Environ. Sci.
12, 3496 (2019).

Li, Z. M. Fichtner, Z. Zhao-Karger, Rechargeable Calcium–Sulfur Batteries Enabled by an Efficient Borate-Based Electrolyte. Small 16, 1–6 (2020).

Zhao-Karger, Y. Xiu, Z. Li, A. Reupert, T. Smok, M. Fichtner, Calcium-tin alloys as anodes for rechargeable non-aqueous calcium-ion batteries at room temperature, Nature Comm.
13, 3849 (2022).
Development of Anode-Free Lithium Metal Batteries
Authors: Hwang Bing-Joe
Published: February 2024

The continuous demand for high energy density storage devices, researchers has focused on a new energy storage system for their practical life. Absolutely, Lithium metal is a best anode candidate for high energy density Lithium Metal Battery (LMB) because it has high theoretical capacity, light weight and much lower negative reduction potential.However, the growth of Li dendrite and low Coulombic efficiency upon Li plating/stripping causes the safety issues and poor cycle life of LMBs because of challenges embedded from the interaction of the Li metal with electrolyte and unstable SEI layer formation. For that reason, people have focused on developing new chemistry/system to improve the energy density, cycle life and safe energy storage system for practical applications. Anode free lithium metal battery (AFLMB) is one of the alternate choices and new system for high energy density storage system because it has no active anode material initially. In addition, the fabrication of AFLMB is simple, low-cost, safe since Li metal is not directly used as an anode. However, since the Li amount is limited and electrolyte decomposition, consuming Li during the SEI formation, the capacity can fade quickly relative to LMB. The dead Li can affect the Coulombic efficiency, polarization, and cycle life of the cell during continues cycles of AFLMB. However, AFLMB is the best system to understand the detail chemistry like quantification of dead Li, polarization effect, electrolyte consumption easily compared to the LMB. In this presentation, various approaches including functional electrolytes and functional coating on Cu surface will be reported to improve the coulombic efficiency, energy density and cycle life for the AFLMB.
A BF3-Doped MXene Dual-Layer Interphase for Reliable Lithium Metal Anode
Authors: Niu Junjie
Published: February 2024

The surface modification of lithium metal anode poses a promising way in reaching high energy-density batteries. Here we introduce a dual-layer interphase that consists of an in-situ formed lithium carboxylate organic layer and an ultra-thin BF3-doped monolayer Ti3C2 MXene on Li metal surface (Shang, Shovon, Wong, Niu. Advanced Materials, 35 (2023) 2210111). The honeycomb-structured organic layer increases the wetting of electrolyte due to the large surface area, leading to a thin solid electrolyte interface (SEI). While the BF3-doped monolayer MXene provides abundant active sites for lithium homogeneous nucleation and growth, resulting in about 50% reduced thickness of inorganic-rich components among the SEI layer. A low overpotential of less than 30 mV over 1000 h cycling in symmetric cells was received. The functional BF3 groups along with the excellent electronic conductivity and smooth surface of the MXene greatly reduce the lithium plating/stripping energy barrier, enabling a dendrite-free lithium metal anode. The battery paired with NMC811 exhibited a high initial Coulombic efficiency (CE) of 82.1%. A high capacity-retention of 175.4 mAh/g at 1.0 C was achieved after 350 cycles. After long 500 cycles, a reliable capacity was still remained while the cell with un-modified Li metal quickly dropped to below 74.2 mAh/g. In a pouch cell with a capacity of 475 mAh, the battery still exhibited a high discharge capacity of 165.6 mAh/g with a capacity retention of 90.2% after 200 cycles, while the cell with pure Li metal decreased to 80.5%.

Keywords: Lithium metal electrode; Lithium ion battery; MXene; Doping
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.
Optimizing Dopant for Enhanced Oxygen-Redox Performance in P2-Na Cathode Materials for Sodium-Ion Batteries
Authors: Cho ManJae , Myung Seung-Taek
Published: February 2024

Recently, there has been a lot of interest in using oxygen-redox-based cathode materials for sodium-ion batteries (SIBs) due to their potential for providing additional capacity in the high-voltage range. However, they have some matter, including fast capacity fading and poor rate capability. Herein, P2-Na0.7[Li0.1Ni0.1Mg0.1Mn0.7]O2 is introduced, an layered oxide cathode material for Na-ion batteries based on oxygen-redox. The effect of Ni doping is improved electrochemical performance. Mg2+ in transition metal layer delivered relatively higher capacity via oxygen redox in high voltage region by comparison with Mg-free P2-Na0.75[Li0.15Ni0.15Mn0.7]O2, showing a specific discharge capacity of 175mAh g-1 with 83% of capacity retention after 100 cycles. This study show how the co-doping of Li, Ni and Mg can impact P2-type layered materials and proposes a novel approach to utilizing Mn-rich cathode materials through oxygen redox, with a focus on optimizing the dopant for sodium-ion batteries.
High Rate Performance of Li Metal Anode in Na-Containing so2-Based Inorganic Electrolyte
Authors: Mun Seung Do , Lee Jiwhan , Choi Seong Hoon , Kim Jun Sik , Kim Seungeun , Kim Hansu
Published: February 2024

Lithium metal anode is one of the best candidates for the next generation energy storage systems due to the lowest electrochemical potential (- 3.04 V vs. standard hydrogen electrode) and the highest theoretical capacity (3860 mAh g-1). However, lithium metal anode have critical problems including dendritic growth of Li deposits during cycling, poor stability of solid electrolyte interface (SEI) on lithium metal anode and severe chemical reaction between Li metal and the electrolyte. Recently, stable artificial interface layers on the Li metal anode have been proposed to solve these problems. In this work, surface modification of Li metal with a Na-containing SO2-based inorganic electrolyte was investigated as an effective way to prevent lithium dendritic growth during cell operation. The surface-modified lithium metal anode effectively prevented the dendritic deposits of Li deposits even at high current density (3 mA cm-2). More detailed reaction chemistry of Li metal with Na-containing inorganic electrolyte will be discussed in the presentation.
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
Synthesis and Characterization of 2,5 Polybenzimidazole-ZrO2 Nanocomposite Membrane Towards Improved Vanadium Redox Flow Battery Performance
Authors: Bhattacharyya Rama
Published: February 2024

Zirconium oxide (ZrO2) nanomaterials were synthesized by hydrothermal method using ZrOCl2,8H2O and KOH as precursors. The as-synthesized ZrO2 was characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), Field Emission Gun Scanning electron microscopy (FEG-SEM), transmission electron microscopy (TEM) and Brunaur-Emmett-Teller (BET) surface analysis. The synthesized ZrO2 nanomaterial is used to prepare composite 2,5 polybenzimidazole (ABPBI) polymer membrane. The nanocomposite membrane was further gone through various characterisation processes as mechanical stability, X-ray diffraction (XRD), contact angle measurement, Electrochemical impedance spectroscopy (EIS) and Field Emission Gun Scanning electron microscopy (FEG-SEM). The influence of ZrO2 nanoparticle for preparing composite polymer membrane to use in Vanadium redox flow battery as a separator was studied. The investigation shows significant improvement in mechanical stability and robustness, enhancement in ionic conductivity of the nanocomposite membrane and excellent battery performance.

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
Sustainable Recovery, Surface Chemical Engineering, and Upcycling of Spent Graphite into Dual-Ion Battery
Authors: Ghosh Shuvajit , Bhar Madhushri , Bhattacharjee Udita , Krishnamurthy Satheesh , Yalamanchili Kali Prasad , Martha Surendra
Published: February 2024

Recycling has become an absolute necessity. Spent Lithium-ion batteries (LIBs) are hazardous waste but a potential source of purified minerals. The industrial focus on LIB recycling is mostly centered on costly and scarce cathode materials recovery. Graphite is often overlooked as it fails to generate useful revenue. Herein, the waste LIBs are recycled following an all-components-recovery route that minimizes cross-contamination. However, the surface of the recovered graphite is covered with solid electrolyte interphase (SEI) formed during its first life application. Solvent wash followed by thermal treatment revives graphite for second-life applications. Three important things to consider here are the interaction of solvent media with the preformed SEI, the role of leftover SEI in forming the second-life SEI, and the effect of regenerated SEI on second-life electrochemistry. Therefore, the nature of the solvent plays a vital role in the overall process. Utilizing water is the go-to alternative but the obtained electrochemistry from water-washed graphite is below the mark. Organic solvent dimethyl carbonate (DMC) modifies the chemical composition of the interphase in such a way that it improves second-life electrochemistry. Strong inorganic acid HCl results in the highest carbon purity and makes recovered graphite suitable for non-electrochemical applications too. Electrochemically superior DMC-washed graphite is repurposed into a dual-ion full cell that delivers an average voltage of 4.5 V and an energy density of 110 Wh kg-1.

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3D Printed Freestanding Electrodes for High Energy Density Batteries
Authors: Romero Cameron Taj , Gordon Kenneth , Liu Zhi , Joseph Karius , Broussard Emily , Fei Ling
Published: February 2024

The global surge in energy consumption, as well as a rise in greenhouse gases, has created an urgent need for high-capacity battery materials to store intermittent, renewable energy sources such as wind and solar. Directly increasing electrode mass loading using the traditional slurry coating fabrication process introduces unavoidable issues such as slowed kinetics and thermal degradation. Freestanding electrodes are a great alternative as they eliminate the need for inactive components (i.e., binder, additive carbon, and current collector) and shorten the fabrication process. In this work, carbon microlattice templates are designed and fabricated through the use of 3D stereolithography, which allows for design flexibility of any shape or geometry, followed by pyrolysis to create porous hard carbon. These hard-carbon templates are then subjected to a ferrocene/sulfur reaction to grow iron sulfide that serves as active material, which has a theoretical specific capacity higher than that of commercial graphite. The design utilizes controlled microchannels that facilitate ion transport through charging and discharging cycles. The addition of FeS led to a specific capacity of 1204.2 mAh g-1 during cycle two with a current density of 500 mA g-1, which is much higher than that achieved with the control carbon template (≈37.3 mAh g-1 at 300 mA g-1). These results will advance the development of composite electrodes as well as shine light on the immense potential to develop high energy density batteries utilizing 3D printing.
Constructing Stable Solid Electrolyte Interphase Using Gel Polymer Electrolytes for Anode-Free Lithium Metal Batteries with Enhanced Cycle Life
Authors: Ban A-Hyeon , Roh Jin-Ah , Kim Hyo-Geun , Bae Woo Jin , Woo Hyun-Sik , Moon Jongseok , Kim Dong-Won
Published: February 2024

Anode-free lithium metal batteries (AFLMBs) have recently emerged as next-generation batteries due to high energy density, reduced cost, and simplified manufacturing process due to the absence of reactive metallic lithium. However, developing high-performance AFLMBs faces several challenges for practical applications, such as low coulombic efficiency and poor cyclability, due to the dendrite growth of lithium and side reactions of lithium with liquid electrolytes. To develop the AFLMBs with long cycle life, it is necessary to attain high coulombic efficiency since there is no excessive lithium to compensate for irreversible Li inventory losses in the AFLMB. Three-dimensional cross-linked gel polymer electrolyte (GPE) can be a good candidate for stabilizing the lithium metal by encapsulating organic solvents in the polymer matrix, leading to reduction of the parasitic reactions between lithium metal and liquid electrolyte, which results in high coulombic efficiency of AFLMBs. In this work, we prepared a cross-linked GPE using a multi-functional cross-linking agent to realize high coulombic efficiency and long cycle life of AFLMBs with LiNixCoyAl1-x-yO2(NCA) cathode (areal capacity of 4.76 mAh cm-2). Moreover, the GPE capable of coordinating with lithium ions could construct stable solid electrolyte interphase by regulating lithium ion solvation structures. Cycling performance was investigated in the voltage range of 3.6 – 4.3 V at 0.5 C rate. The Cu/GPE/NCA cell exhibited a capacity retention of 80% after 150 cycles, which was higher than that of AFLMB with liquid electrolyte. Electrochemical characterization and spectrometry were performed to investigate how the GPE could improve the cycling performance of AFLMBs.
Enhancing Cycle Life of Lithium Metal Batteries By Regulating Solid-Electrolyte Interphase Using Gel Polymer Electrolyte
Authors: Kim Ji-Wan , Oh Myung-Keun , Kim Yeona , Kwon Eun-Ji , Seo Samuel , Kim Wonkeun , Ryu Kyounghan , Kim Dong-Won
Published: February 2024

Lithium metal with high theoretical capacity and low redox potential is one of the promising anode materials for high energy density batteries. However, the lithium metal has safety problems and poor cycling performance, due to the growth of Li dendrite and side reactions between Li and electrolytes. One of the most effective strategies to stabilize Li metal is forming robust solid-electrolyte interphase (SEI). Recently, anion-derived and inorganic-rich SEI is known to be stable and ionic conductive, leading to good cycling stability. One of the most popular strategies to form durable SEI is to use the localized high-concentration electrolytes (LHCE) which construct an anion-derived SEI layer on Li metal. In this work, we synthesized LHCE-based gel polymer electrolytes to form a stable SEI layer and enhance cycling stability. Small amount of cross-linking agent was added into dimethoxyethane (DME)-based LHCE when synthesizing gel polymer electrolyte. The functional groups in cross-linking agents increase Li+ and anion interaction in the gel polymer electrolytes, resulting in formation of the stable SEI layer. The solvation structure and chemical composition of the SEI layer were investigated by density functional theory (DFT) calculation and spectroscopic analyses such as FT-IR, Raman, and XPS. The Li/NCM811 cells with LHCE-based gel polymer electrolyte were assembled for the cycling test, and they exhibited superior cycling performance than liquid electrolyte-based cells.
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.

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Computer Simulation Study of Lithium and Oxygen Adsorption on Ruthenium Dioxide (110) Surface
Authors: Maenetja Khomotso Portia , Chokoe Kgakgathu Alfonia , Ngoepe Phuti Esrom
Published: February 2024

Metal oxides are widely considered as excellent catalysts in lithium-air batteries to promote the production of stable discharge products and achieve superior electrochemical performance. The lithium–air (Li–air) battery is a metal–air electrochemical cell or battery chemistry that uses oxidation of lithium at the anode and reduction of oxygen at the cathode to induce a current. Despite various studies exploring the use of metal oxides as effective catalysis, the catalytic activity of ruthenium oxide (RuO2) towards lithium and oxygen ions is not fully understood. In this work, we investigate the adsorptions of lithium and oxygen on the RuO2 (110) surface using density functional theory (DFT) method. Due of the size of the supercell, and assuming that oxygen atoms occupy bulk-like positions around the surface metal atoms, only five values of (gamma) Γ are possible if constraint to a maximum of 1 monolayer (ML) of adatoms or vacancies: Γ= 0 surface is the stoichiometric surface, Γ= 1, 2 are the partially and totally oxidised surfaces, and Γ=-1, -2 are the partially and totally reduced surfaces. The addition of two oxygen atoms revealed the most stable adsorption energy is the mono-clear followed by bridging configuration. The lithium orientation between two bridging oxygen and in plane oxygen (bbi) orientation is much more stable, thus lithium generally prefers to adsorb where it will be triply coordinated to two bridging oxygen atoms and one in plane oxygen atom. Rutile RuO2 has been widely considered as an excellent catalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in non-aqueous.
Investigating the Impedance of an Iron/Iron Redox Flow Battery at Different State of Charge Conditions – a Distribution of Relaxation Times Analysis
Authors: Challuri Sai Venkata Akhil Kumar , Noack Jens
Published: February 2024

New energy storage technologies are needed to offset the erratic power supply of renewable energy sources due to the rising global energy demand and the urgency of climate change action. The Iron/Iron redox flow battery is a viable contender for large-scale energy storage, even if there are still issues with operational parameters and efficiency. Due to the positive electrode's moderate pH and low voltage, which preserves minimum toxicity and aggressivity, iron is a very affordable active material, making it feasible to develop inexpensive energy storage systems and batteries. The Electrochemical impedance spectroscopy technique was utilized to understand the degradation of the iron/iron redox flow battery during charging and discharging operation modes. However, discriminating between processes occurring at similar time scales is difficult since they overlap in the generally used Nyquist or Bode representation. Distribution of relaxation times (DRT) analysis tackles this issue by converting the EIS data with respect to the time constants of the individual processes. Individual processes such as electrochemical reactions inside the iron/iron redox flow cell, transport processes through porous structures, and iron ion transport were investigated.

The impedance measurements were carried out to evaluate the ohmic resistance during the charging and discharging phases of the iron/iron redox flow battery with varied states of charge ranging from 0-100% while charging and 100-0% while discharging. In this series, a DC offset load of 100 mA in the charging and discharging directions was used to test the resistance differential associated with the battery's state of charge. In the charging phase of the battery of three DC offset load parameters, the iron ions were transported faster in the process while the state of charge of a battery increased at lower frequencies. The impedance increased when the state of charge decreased at a higher frequency range, involving the iron ions transported through the negative half-cell in an iron/iron redox flow battery. The overall ohmic resistance in the charging phase of the battery decreased up to 6 % until the battery was fully charged, but in discharging phase, the overall ohmic resistance increased to 2 %. This indicated that the DC offset load in the charging and discharging direction were dependent on the battery's state of charge.

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