bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Synthesizing Cathode Precursors Directly from Lithium Ores
Authors: Wang Shilong , Szymanski Nathan , Zeng Yan , Ceder Gerbrand 
Published: December 2024

Abstract:

With the increasing demand of lithium (Li) used for energy storage, there is a need for diversified Li sources beyond brines. Among the minerals that can satisfy this need, spodumene is most often used for its high Li content and natural abundance. However, the traditional approach to process spodumene is costly and energy-intensive, requiring that the mineral be transformed from its naturally occurring α phase into the more reactive β phase at temperatures exceeding 1000 °C [1, 2]. Acid leaching is then used to extract Li, followed by neutralization to precipitate Li in the form of Li2CO3, a common precursor for the synthesis of Li-ion battery cathodes. Recently, we have developed an improved procedure to extract Li directly from α-spodumene, which can be performed at lower temperatures and avoids the use of acids. Li2CO3 can be formed with > 90% yield at 750 °C by reacting α-spodumene with inexpensive additives. Following its extraction from spodumene, Li2CO3 can be isolated with high purity by washing the sample using deionized water [3]. The Li extraction process introduced above presents a low-energy and acid-free route to obtain Li2CO3 directly from spodumene, thereby fostering a more sustainable and efficient utilization of natural minerals to produce precursors that are essential for battery industry. We will also demonstrate how the in-situ formation of Li2CO3 opens new opportunities for the direct synthesis of battery materials from raw ores (α-spodumene).

References:

[1] Karrech, A., et al., A review on methods for liberating lithium from pegmatities, Minerals Engineering, 2020. 145.
[2] Yelatontsev, D. and Mukhachev A., Processing of lithium ores: Industrial technologies and case studies – A review, Hydrometallurgy, 2021. 201.
[3] Shilong, W., Nathan, S., et al., Direct lithium extraction from α-spodumene through solid-state reactions for sustainable Li2CO3 production, under review.
(Invited) A Non-Stabilized Supersaturated High-Energy-Density Storage Concept for the Redox Flow Battery and Its Demonstration in an H2-V System
Authors: Mouron Spencer T , Nguyen Trung Van 
Published: December 2024

Redox flow battery (RFB)-based storage systems have the unique feature of separating power generation from energy storage, allowing individually sized systems uncoupling power from capacity. RFBs can be used for days-long energy storage, but because of the low solubility of most ions and molecules in both aqueous and non-aqueous solvents,[1,2] scaling these RFB systems for days-long applications requires significant storage tanks and floor area.
Our team has been working on a new storage method for Vanadium electrolytes that significantly increases the energy storage density while still maintaining the traditional flow battery design.[3] This method involves storing the reactants as both soluble ions and as undissolved solids, only allowing liquid-containing soluble ions to circulate through the battery. To achieve this, a solid form of Vanadium salt must be precipitated within the storage tanks, with an applied temperature swing to dissolve this solid and keep the electrolyte below saturation level for transport to the flow battery. To run this system without any form of external heating or cooling, we propose to allow saturated electrolyte to enter the flow battery during operation. This presentation will discuss the operation of a V-H2 redox flow battery system operating at 2.5 M total vanadium concentration (above the 1.8M solubility limit of VOSO4)[4] and its comparison to a more traditional sub-saturated system at 2.5M and 1.5M total vanadium ion concentrations respectively.

References

[1] V. Singh, S. Kim, J. Kang, and H. R. Byon, Nano Res.,
12, 1988-2001 (2019).
[2] K. Gong, F. Xu, J. B. Grunewald, X. Ma, Y. Zhao, S. Gu, and Y. Yan, ACS Energy Lett.,
1, 89-93 (2016).
[3] Y. Li and T. V. Nguyen, Provisional US patent application number 62/941,064 filed 2019/11/27, International Application No. PCT/US20/61455 filed 2020/11/20 (WO2021108244A1).
[4] Skyllas‐Kazacos, M.; Peng, C.; Cheng, M. Evaluation of Precipitation Inhibitors for Supersaturated Vanadyl Electrolytes for the Vanadium Redox Battery. Electrochem. Solid-State Lett. 1998, 2 (3), 121. https://doi.org/10.1149/1.1390754.

Figure 1
(Invited) A Versatile Reference Electrode for Lithium Battery Use
Authors: Koch Brian , Gao Jing , Zhang Anne , Garrick Taylor R. 
Published: December 2024

A thin, porous, separator-supported reference electrode disposed between an anode and cathode is proposed as a practical, implementable solution for measuring individual electrode potentials in a commercial lithium ion cell. Its precise placement at the midpoint of the cell stack and permeable layer design allow for a simple formula for the calculation anode and cathode potential, while affecting the electrochemical performance of the cell only to the extent of adding one extra separator.
In this study, we introduce a separator-supported reference electrode for both laboratory use and real-time, direct-feedback battery control systems in electric vehicles. Extraction of electrode kinetic parameters and electrode-level control of DC fast charge are shown for an NCMA/Graphite 1Ah pouch cell to demonstrate the simplicity, fidelity, and robustness of the reference electrode design.
References
1. T. R. Garrick, J. Gao, X. Yang, and B. J. Koch. J. Electrochem. Soc., 168 010530 (2021)
2. T. R. Garrick, Y. Zeng, J. B. Siegel, and V. R. Subramanian, J. Electrochem. Soc., 170, 113502 (2023)
3. J. Gao, B. J. Koch, and T. R. Garrick. "Electrochemical Systems, Methods, and Devices Using Stacked Electrode Assemblies with In-Stack Sensor Arrays." U. S. Patent App. No. 17/479,558
4. H. Zhang, T. R. Garrick, and B. J. Koch. "Method and System for Charging a Battery" U. S. Patent App. No. 17/894,691
5. J. Gao, B. J. Koch, T. R. Garrick, and W. Zeng. "System and Method for In-Situ Mapping on Electrode Potential and Thermal Distribution" U. S. Patent App. No. 17/891,120
6. B. J. Koch, A. McAllister, and R. S. Conell. "Reference Electrode" U. S. Patent 10,439,256
Room Temperature Modification of Carbon Cloth for Water Splitting
Authors: Dalla Benetta Marilia Barreto , Breslin Carmel B , Dempsey Eithne 
Published: December 2024

The energy production sector has faced many challenges, especially regarding the environmental impacts caused using fossil fuels. Renewable hydrogen, generated via electrolysis of water, has emerged as a possible solution to reducing global reliance on fossil fuels as a source of energy. Many emerging catalysts are made using hydrothermal synthesis, demonstrating good water-splitting performance. However, the methods used to make such materials can be time and energy-consuming, while generating a significant quantity of chemical waste, which remain in the environment for long periods. This study focuses on the development of a new environmentally benign, solvent-free, room-temperature synthesis design taking advantage of abundant, low-cost materials.
In the first stage of this study, a room temperature deposition of Molybdate (Mo) on the surface of Nickel Foam (NF) was identified. This material resulted in a very good performance in relation to the oxygen evolution reaction (OER). However, NF is an effective catalyst for water splitting, making it challenging to discriminate the effectiveness of immobilized electrocatalysts and the formation of oxides can give false results. To address these issues, in the second phase of the work, carbon cloth (CC) was used as a substrate due to its attractive features of low cost, porosity, and lack of catalytic performance in the absence of modification.
Copper was incorporated on the CC by electrodeposition and porous copper was formed by hydrogen bubble dynamic. The Copper Foam/ Carbon cloth (CF/CC) was further modified by this novel one-pot room temperature synthetic approach. CF/CC presented a significant improvement relative to its bare form. Performance data showed good current density, impressive onset potentials, good Tafel slopes, low impedance, and good stability. Both HER and OER were tested in this study. 1–3

1 H. C. Shin and M. Liu, Chemistry of Materials, , DOI:10.1021/cm048887b.
2 M. Mottakin, V. Selvanathan, M. Ariful Islam, H. Almohamadi, N. H. Alharthi, S. Yoshimura and M. Akhtaruzzaman, Chem Asian J, , DOI:10.1002/asia.202300532.
3 P. Wang, J. An, Z. Ye, W. Cai and X. Zheng, Front Chem, , DOI:10.3389/fchem.2022.913874.

Figure 1
Ultrasonic Monitoring of Li-Ion Batteries
Authors: Milano Lorenzo , Magagnin Luca 
Published: December 2024

To improve the accuracy of lithium-ion battery (LIB) monitoring, a recent trend involves using data that reflect changes in material properties caused by the intercalation and deintercalation of lithium ions. By focusing on specific layers within the battery, a broader array of information can be obtained to determine its state of charge (SoC) and health (SoH) locally. Since the speed of sound changes depending on the material properties and traveling waves are partly reflected at each interface, ultrasonic analysis (UA) offers the potential to enhance LIB monitoring by providing real-time, through-thickness data.
In this study, NMC-graphite LIBs were cycled and monitored using UA in pulse-echo and through-thickness modes with a center frequency of 5 MHz. The primary focus was to examine the effect of cycling on each peak's intensity and shift on the time axis. An NMC631-graphite battery was monitored in pulse-echo mode while cycling according to a fixed-capacity protocol. Results showed the appearance of two sets of peaks appearing in different position on the time axis when the end of discharge and end of charge, respectively, are approaching. The time shift and amplitude of each peak had the same periodicity of the cycling protocol, moreover, such variations are compatible with the evolution of materials properties induced by lithiation.
Following this, the battery was cycled fixing the charge/discharge capacity and varying its value at each cycle (50, 20, 300, 400 mAh) while monitored in through transmission. Here, rather than focussing on peaks position and intensity, the frequency domain analysis revealed three main waves composing the signal. The one with lowest frequency became progressively more influent while discharging, the one close to the center frequency did not show dependency on the stored charge while the highest in frequency had opposite trend to the first one. Interestingly, the waves with lowest and highest frequency had a Fourier coefficient which was quasi-linearly dependent on the stored charge.
Overall the main outcomes of this work are:
I. The possibility to observe different battery layers directly from the waveform.
II. The Fourier coefficient of two main frequencies is a linearly dependent on the stored charge.
Positive-to-Negative Electrode Cross-Talk in Lithium-Ion Batteries
Authors: Rinkel Bernardine L. D. , McCloskey Bryan D. 
Published: December 2024

Electrolyte decomposition reactions are the dominant source for capacity fade in (commercial) lithium-ion batteries. Even though the parasitic reactions at the graphite electrode have been identified as a major source for this, the observed capacity fade also appears to be strongly tied to the choice of material for the positive electrode, indicating that the positive electrode may indirectly or partially contribute to the overall capacity fade. In particular, electrolyte decomposition products formed at the positive electrode may diffuse or migrate to the negative electrode, where they can react further or damage the SEI, in a process called “electrode cross-talk”. One product could initiate a disproportionate number of secondary reactions, leading to increased degradation (more than what would be expected from a single molecule). Unfortunately, up until recently, the electrolyte oxidation reactions at the positive electrode and specifically the products that are formed, were unknown, making it impossible to investigate any cross-talk processes and their contribution to battery degradation. Fortunately, with the recent identification of soluble decomposition products formed at positive electrodes, 1,2 it has now become possible to explore positive-to-negative electrode cross-talk.
In this work, the impact and reactivity of electrolyte decomposition products formed at layered transition metal oxide electrodes on the SEI were studied. First, a representative SEI was formed on graphite electrodes, after which it was carefully exposed to various decomposition products (e.g., acids: HF, formic acid; alcohols: methanol, acetals, etc.). After exposure, solution NMR spectroscopy was used to detect newly formed products, as well as dissolution of the existing SEI. Operando gas measurements were employed to assess the integrity and composition of the SEI after exposure. The experimentally detected soluble and gaseous products were then used to gain mechanistic insights into inter-electrode reactions. The findings on positive to negative electrode cross-talk processes will further the understanding of why lithium-ion batteries degrade, and will enable the design of highly effective strategies to mitigate degradation.
(1) Rinkel, B. L. D.; Hall, D. S.; Temprano, I.; Grey, C. P. Electrolyte Oxidation Pathways in Lithium-Ion Batteries. J Am Chem Soc
2020, 142 (35), 15058–15074. https://doi.org/10.1021/jacs.0c06363.
(2) Rinkel, B. L. D.; Vivek, J. P.; Garcia-Araez, N.; Grey, C. P. Two Electrolyte Decomposition Pathways at Nickel-Rich Cathode Surfaces in Lithium-Ion Batteries. Energy Environ Sci
2022, 15 (8), 3416–3438. https://doi.org/10.1039/d1ee04053g.
Towards Understanding the Structure and Dynamics of Localized High-Concentration Battery Electrolytes
Authors: Hockmann Anne , Diddens Diddo , Cekic-Laskovic Isidora , Schönhoff Monika 
Published: December 2024

In recent years high-concentration liquid electrolytes (HCEs) received much attention in the battery research due to the evident performance advancement achieved in lithium-based batteries. HCEs offer lots of advantages comprising, among others, broad electrochemical stability window, current collector protection, high safety, an effective solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI) formation, and therefore a high rate capability and stable galvanostatic cycling.[1] However, due to the high conducting salt content, HCEs are very viscous thus resulting in low ionic conductivity. This is why the concept of localized high-concentration electrolytes (LHCEs) was developed and first published by Chen et al. in 2018.[2] Here, a third component next to salt and solvent, the diluent, is added to the system to reduce the viscosity without participating in the ion solvation. With this addition, a heterogeneous structure consisting of conducting salt-rich and diluent-rich phases is created. Thereby, the local environment of the ions, which is responsible for the described benefits of a HCE, remains unchanged and the main disadvantage, the low ionic conductivity, is improved.
However, the structural heterogeneity of the LHCEs, the complexity of the composition of conducting salt- and diluent-rich phases, and their interfacial interactions require further research to gain a profound understanding of the structure and ion dynamics in order to reach the full potential of this type of electrolyte formulation. Therefore, in this work a comparative study of LHCEs based on lithium bis(trifluoro-methanesulfonyl)imide (LiTFSI) or lithium bis(fluorosulfonyl)imide (LiFSI) as the conducting salt, dissolved in 1,2-dimethoxyethane (DME), and diluted with 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) was carried out. A combination of selected complementary spectroscopic methods, namely NMR, Raman, and impedance spectroscopy supported by molecular dynamics (MD) simulations, was used to study the effects of an increasing dilution on the two types of electrolyte formulations. We show that varying the anion structure already has a significant impact on the conducting salt/diluent-interface influencing the lithium coordination and dynamics: While the TFSI- anion appears to interact with the diluent at the interface resulting in a higher degree of ion dissociation and increased dynamics in the conducting salt-rich phase, the FSI- anion leads to stronger ionic interactions and a more compact conducting salt-phase with slower dynamics.

References

Yamada, J. Wang, S. Ko, E. Watanabe, A. Yamada, Nat Energy
4 (2019), 269–280.

Chen, J. Zheng, D. Mei, K. S. Han, M. H. Engelhard, W. Zhao, W. Xu, J. Liu, J.-G. Zhang, Adv.
Mater.
30 (2018), 1706102.

Figure 1
Aqueous Processing of Ni-Rich Layered Oxide-Based Cathodes: Evaluating Strategies Via Additives, Binders and Coatings
Authors: Albers Simon , Winter Martin , Kasnatscheew Johannes 
Published: December 2024

The growing demand of batteries for electric mobility enhances the overall environmental impact of battery production. Among the different cathode cell chemistries, the Ni-rich layered oxide LiNi
x
Co
y
Mn
z
O2 (NCM)-based cathode active material (CAM) is regarded to have the lowest global warming potential of around 75.5 kg CO2-Eq/kWh1, whereas ≈25 % is attributed to cell manufacturing. The global warming potential could be reduced by 16 % via aqueous cathode electrode production2, as water instead of N-methyl-2-pyrrolidone (NMP) as processing solvent is generally advantageous in several aspects e.g., not necessitating solvent recovery. However, Ni-rich NCMs are water sensitive and prone to structural degradation, leading to e.g., particle cracking and surface layer reconstructions. Consequently, lithium and transition metals dissolve in the aqueous media forming soluble (such as LiOH and Li2CO3) and insoluble (such as NiOOH) species.3 The formation of LiOH leads to an increase in pH and can cause corrosion of the aluminium current collector.
Promising strategies for aqueous processing are either based on CAM coating, processing aspects (e.g., functionalized binders, electrode paste additives) or electrolyte additives. A common processing additive is phosphoric acid, which is aimed to lower the pH, protect the aluminium current collector, and form a protective Li3PO4 layer on the NCM particle surface. However, further investigations are required to gain a full understanding of the NCM interphase changes and to evaluate other interphase engineering strategies to overcome the remaining obstacles.
In this study, the well-known strategies are evaluated with respect to electrochemical performance of LiNi83Co12Mn05O2||Graphite cells. Each strategy is applied within a characteristic time scale of NCM path, i.e., from synthesis to end-of-life (see scheme 1), and reveal characteristic advantages and disadvantages on cathode particle degradation and interphase formation.
References

M. Mohr, J. F. Peters, M. Baumann and M. Weil, Journal of Industrial Ecology,
24(6), 1310–1322 (2020).

K. Shen, Q. Zhai, Y. Gu, W. Wang, H. Cao, M. Hauschild and C. Yuan, Resources, Conservation and Recycling,
198, 107152 (2023).

M. Hofmann, M. Kapuschinski, U. Guntow and G. A. Giffin, J. Electrochem. Soc.,
167(14), 140535 (2020).

Figure 1
Stabilizing Lithium Metal Anode and Conversion Cathode Interphases for High Energy Density Batteries
Authors: Lopez Jeffrey 
Published: December 2024

Lithium metal batteries offer great promise for higher energy density, but are presently limited by significant side reactions, poor quality deposition, and the potential to form hazardous dendrites. This is especially true when paired with conversion cathodes, which could potentially result in cells with specific energy > 700 Wh/kg. In this presentation, recent advances made toward high energy full cells will be discussed. A particular emphasis will be placed on the electrode-electrolyte interphases that form in these devices in high performance localized high concentration electrolytes (LHCE).
Specifically, we employ electron paramagnetic resonance (EPR) spectroscopy to identify radical intermediates and operando surface enhanced IR absorption (SEIRA) spectroscopy to clarify electrolyte reduction/oxidation mechanisms. Operando SEIRA provides detailed information about the organic components of the solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI) on lithium metal anodes and FeF2 cathodes respectively. Common SEI components from high Coulombic efficiency fluorinated electrolytes are identified and mechanisms will be discussed in the context of moving toward more environmentally friendly fluorine-free electrolytes. Furthermore, strategies to stabilize FeF2 conversion cathodes through interphase modification to produce more mechanically robust composite electrodes and improve cycling stability will be discussed. With the understanding developed through this holistic approach, we provide new insight into electrolytes and the formation of interphase components that promote stable cycling of lithium metal- FeF2 full cells.
Approach to Regulating Crystal Nucleation for High-Performance Lithium-Chalcogen Batteries
Authors: Kim Mihyun , Yu Seung-Ho 
Published: December 2024

Chalcogen cathodes, with their high theoretical energy density, have shown promise for advancing lithium-ion battery (LIB) technology. However, the structure of chalcogen crystals significantly impacts cycle performance and could constrain rate capability due to their intrinsic insulating nature. Therefore, this study explores approaches to regulate the nucleation of chalcogen elements to enhance cycle performance beyond that of lithium-sulfur batteries.
We investigate the dissolution and deposition mechanisms of the chalcogen cathode materials, as well as nucleation phenomena by using advanced techniques such as operando X-ray diffraction (XRD) and transmission X-ray microscopy (TXM). Particularly, operando TXM imaging captures the growth of chalcogen crystals, shedding light on their nucleation behavior. Expending on these discoveries, we control the crystal nucleation of the chalcogen cathodes, resulting in impressive specific capacity and improved rate capability.
This work offers valuable insights into the chalcogen crystal nucleation, paving the way for high-performance lithium-sulfur batteries with improved energy densities and rate performance.

Figure 1. The scheme of the chalcogen crystal growth mechanism and the corresponding cycle performance at a current density of 1.0 A g-1.

Figure 1