bluuebunny/crossref_metadata_2025_split huggingface dataset:
Li3InCl6-Coated High-Voltage Cathodes for Thiophosphate-Based Solid-State Li Batteries
Authors: Jin Feng , Fadillah Laras , Mehraj Ud Din Mir , Rettenwander Daniel 
Published: February 2024

Solid-state Li batteries are pursued as potentially safe and stable high-energy storage systems. However, key issues remain unsolved, impeding the practical realization.[1] One of the fundamental reasons for the failure of these batteries is likely the instability of solid-state electrolytes, such as Li6PS5Cl, towards high voltage cathodes. To mitigate the interface instability issues coating materials that prevent the decomposition of the solid-state electrolytes without limiting the ionic transport across them are thus urgently warranted.[2,3] Halides have been shown to have excellent high voltage stability up to 4.2 V in combination with moderate Li-ion conductivities of the order of magnitude ~10-3 S cm-1.[4]Combining the properties of halides with sulfides, hence, could be a promising strategy to enable room temperature solid-state Li batteries. Therefore, we synthesized nano-sized Li3InCl6 powder by mechanochemistry.Thereafter, Li3InCl6 was coated onto micrometer-sized LiNi0.8Co0.15Al0.05O2 (LIC@NCA) cathode particles using mechanofusion technique. The thickness and uniformity of the coating were investigated using FIB-SEM and TEM. The coating thickness has been found to be as thin as 200 nm nanometers fully covering the NCA particles. Finally, LIC@NCA particles have been tested in a solid-state Li batteries using Li:In-alloy as anode and Li6PS5Cl as SSE. Cells with LIC@NCA show a significant improvement (from 60 mAh/g to 150 mAh/g) in respect of the initial capacity loss and capacity fading compared to the pristine NCA.

References

[1] Janek, J. and Zeier, W.G., 2016. A solid future for battery development. Nat Energy, 1(9), 1-4.
[2] Lewis, J.A., Lee, C., Liu, Y., Han, S.Y., Prakash, D., Klein, E.J., Lee, H.W. and McDowell, M.T., 2022. Role of Areal Capacity in Determining Short Circuiting of Sulfide-Based Solid-State Batteries. ACS
Appl
Mater
I
nterfaces, 14(3), 4051-4060.
[3] Zeng, D., Yao, J., Zhang, L., Xu, R., Wang, S., Yan, X., Yu, C. and Wang, L., 2022. Promoting favorable interfacial properties in lithium-based batteries using chlorine-rich sulfide inorganic solid-state electrolytes. Nat commun, 13(1), 1-13.
[4] Li, X., Liang, J., Luo, J., Norouzi Banis, M., Wang, C., Li, W., Deng, S., Yu, C., Zhao, F., Hu, Y., Sham, T.-K., Zhang, L., Zhao, S., Lu, S., Huang, H., Li, R., Adair, K. R., Sun, X. Air-stable Li3InCl6 electrolyte with high voltage compatibility for all-solid-state batteries. Energy Environ. Sci., 2019, 12, 2665-2671.

Acknowledgement

We acknowledge financial support by Austrian Federal Ministry for Digital and Economic Affairs, the National Foundation for Research, Technology and Development and the Christian Doppler Research Association (Christian Doppler Laboratory for Solid-State Batteries).
Potential and Limitations of Research Battery Cell Types for Electrochemical Data Acquisition
Authors: Smith Anna , Stüble Pirmin , Hofmann Andreas , Leuthner Lea , Jeschull Fabian , Mereacre Liuda 
Published: February 2024

Developing new electrode materials or electrolytes for lithium-ion batteries requires reliable electrochemical testing thereof. In academic research, coin-type cells and small pouch-type cells are commonly being assembled for this purpose. In our study [1], using commercial highly homogeneous and robust LiNi0.33Mn0.33Co0.33O2 (NMC111) cathodes, graphite anodes and 1M LiPF6 in EC/DMC with 3% VC as the electrolyte, four experienced researchers from the Institute for Applied Materials at Karlsruhe Institute of Technology assembled a variety of coin cells within a round robin test. For different cell building parameters, the battery lifetimes systematically varied from a few hundred to well over 2000 cycles before a capacity retention of 80 % was reached. As a benchmark, the same electrodes and electrolyte were incorporated as single- and multi-layer electrode stacks into pouch-type cells and reach almost 4000 cycles with a rate of 1 C.
Missplacing of electrodes and varying amount of electrolyte within a coin-cell were already addressed as performance influencing factors in the literature. In this study, one clear outcome with high impact on previously collected electrochemical data on coin cells, is that the steel grade of cell parts, as well as the in-housed total height of the electrode stack have dramatic influence on cell lifetime and the quality of the acquired electrochemical data. We present our best practice for coin cell manufacturing resulting from the round robin test. Further, it is shown that inappropriate testing conditions like poor cell contacting and cycler settings have additional impact on data collection. In this regard, we emphasize essential parameters for obtaining high quality data.
Additionally, using the same electrodes, we show direct rate performance differences of calendered vs. uncalendered electrodes, as well as half vs. full-cell test results by means of rate capability and long-term cycling stability. While compression of anodes is less crucial for rate capability, substantial differences are measured in case of the cathodes, highlighting the importance of sufficient cathode densification. Moreover, for long-term capacity retention studies, it is demonstrated that electrode densification of both, cathode and anode is crucial for high long-term capacity retention.
Our results are bridging the gap between lab research and industry-type battery cells. It is shown how key performance parameters can be projected from corresponding lab scale battery cell data, if certain important criteria are met vs. where the projections have their limits.
[1] A. Smith, P. Stüble, L. Leuthner, A. Hofmann, F. Jeschull and L. Mereacre, Batteries & Supercaps 2023, e202300080.

Figure 1
Crossover Understanding of a Hydrogen Peroxide Electrosynthesis Device By Combining Oxygen Reduction and Organics Oxidation Reaction
Authors: Ding Penghui , Vagin Mikhail Yu. , Gueskine Viktor , Crispin Xavier 
Published: February 2024

Hydrogen peroxide (H2O2) is a highly useful and green liquid chemical for daily life and industry. It is traditionally employed in wood industry, food packaging, fine chemicals synthesis and environmental depollution. Moreover, it is recently considered in the context of energy storage and conversion such as metal–hydrogen peroxide batteries since the world is trying to find high energy density batteries to replace lithium-ion batteries for electric vehicles and electrified aircraft [1].
Electrochemical production of H2O2 driven by cheap renewable electricity has emerged recently as an alternative to non-sustainable anthraquinone oxidation (AO) process. The recent surge of H2O2 electrosynthesis studies is mainly focused on advanced H2O2 production catalyst design aiming at achieving high activity and selectivity during the last couple of years [2]. As an essential part of H2O2 electrochemical reactors, anode reaction/process is given very little attention among investigators until recently. Water oxidation is the most used anodic reaction, but it suffers from high energy input, the use of expensive catalyst, and low-priced oxygen gas generation. This problem might be mitigated by using alternative organics oxidation processes with the possible generation of value-added products [3]. In order to be economically viable for these systems above, the organics in anode reservoir should not transport to the cathode part through the membrane. However, organic molecules crossover has already been identified in direct alcohol fuel cells and CO2 electrolyzers. Such organics crossover, to the best of our knowledge, has never been considered in previous reports on hydrogen peroxide electrosynthesis devices.
We use conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) for ORR via a two-electron pathway to H2O2. 4,5-Dihydroxy-1,3-benzenedisulfonic acid disodium salt monohydrate (BQDS) was used as a model organic molecule since its oxidation process does not require catalysts as a typical electrolyte used in redox flow batteries. We investigated electrolyte and electric field effects on crossover and H2O2 production.
[1] Chem Catal. 2023, 3, 100568
[2] Nat. Rev. Chem.2019, 3, 442
[3] Nat. Energy
2021, 6, 904
Application of Industrial-Scale Lithium Sulphate Electrolysis in Battery Recycling
Authors: Boyd Tony , Brereton Clive , Moulson Jeremy , Wolfs Warren , GLynn Luke 
Published: February 2024

As the world charges towards electrification and sustainable transportation, it is critical that the entire supply chain is equally sustainable. Industrial processes must be tailored towards circular processes in which emissions and effluents to the environment are minimized, if not eliminated altogether. When it comes to the production of battery grade lithium hydroxide monohydrate, a critical component of lithium ion batteries (LIBs), and the recovery of the lithium in spent LIBs. NORAM Electrolysis Systems Inc (NESI) has developed electrochemical technologies in which effluents are greatly reduced.
NESI has developed a flexible, multi-compartment industrial electrolyser for salt splitting (NORSCAND®) applications including electrolysis of lithium sulphate to produce battery-grade lithium hydroxide (LHM). This electrolysis step can be used for the initial production of LHM or for recovering the LHM from recycling LIBs. In either case sulphuric acid is a by-product of the electrolysis process and it can then be recycled for dissolution of black mass in battery recycling processes or for e.g. SX regeneration. In both cases the incorporation of electrolysis in the flowsheet eliminates effluent streams.
This presentation will outline the product quality and environmental benefits of electrolysis applied as part of a battery recycling flowsheet. It will outline the approach to electrolyser scale-up and present test and performance data from industrial-scale application.

Figure 1
Electrochemically Mediated Amine Regeneration for Efficient CO2 Separation: Development and Characterization of Blend Electrolytes
Authors: Hassan Ahmad , Rahimi Mim 
Published: February 2024

Climate change mitigation necessitates the development of effective carbon dioxide (CO2) separation technologies. A wide range of electrochemical processes were recently developed for CO2 separation from various sources, including high concentration streams such as power plant flue gas and dilute streams like air [1]. Our focus is on the electrochemically mediated amine regeneration process, which is inspired by the conventional amine scrubbing process. This novel electrochemical approach offers a sustainable and potentially lower energy alternative for CO2 separation, with reduced absorbent degradation rates [2-4]. In this presentation, we discuss our latest findings on absorbent development, with a primary focus on the electrochemical aspects. We have tested several blended amine electrolytes and investigated their impact on the electrochemical performance of the system. Key parameters, such as resistance components and heterogeneous kinetic rate transfer, were examined using electrochemical impedance spectroscopy (EIS) and rotating disk electrode (RDE) techniques, respectively. Our results demonstrate significantly improved electrochemical performance for the newly developed blend electrolyte compared to benchmark single amine systems. Furthermore, we have successfully designed and implemented a large-scale continuous electrochemical cell using the novel electrolyte formulation. This system has demonstrated efficient and continuous CO2 separation from simulated industrial power plant flue gas, paving the way for sustainable CO2 separation technologies.
References:
[1] Rahimi M, Khurram A, Hatton TA, Gallant B. Electrochemical carbon capture processes for mitigation of CO2 emissions. Chemical Society Reviews. 2022;51:8676-95.
[2] Rahimi M, Diederichsen KM, Ozbek N, Wang M, Choi W, Hatton TA. An electrochemically mediated amine regeneration process with a mixed absorbent for postcombustion CO2 capture. Environmental Science & Technology. 2020;54:8999-9007.
[3] Wang M, Rahimi M, Kumar A, Hariharan S, Choi W, Hatton TA. Flue gas CO2 capture via electrochemically mediated amine regeneration: System design and performance. Applied Energy. 2019;255:113879.
[4] Rahimi M, Zucchelli F, Puccini M, Alan Hatton T. Improved COA capture performance of electrochemically mediated amine regeneration processes with ionic surfactant additives. ACS Applied Energy Materials. 2020;3:10823-30.
Investigating the Effect of Alkali Metal Cations on Kolbe Electrolysis
Authors: Ashraf Talal , Mul Guido , Mei Bastian 
Published: February 2024

Carboxylic acids, a major fraction of pyrolysis oil can be transformed electrochemically in alkanes and alcohols by Kolbe and Hofer Moest reaction. The selectivity of electrochemical decarboxylation depends on various factors, i.e. electrode material and reaction conditions (supporting electrolyte, pH and current densities) which are well explained in the literature1–3. Alkali metal cations (Li+, Na+, K+, Cs+) are widely considered inert,4 nevertheless in recent studies, a significant influence on different electrochemical reactions such as methanol5,6, ethanol7, and formic acid8 oxidation is reported. It is assumed that oxygenated species present on the electrode surface form (strong/weak) non-covalent interaction with the alkali metal cations.
In this work, we studied the electrochemical oxidation of acetic acid (Kolbe electrolysis) and explored the influence of monovalent alkali metal cations (Li+, Na+, K+ and Cs+). It is observed that the product distribution and overall electrochemical activity are influenced by the presence of cations with K+ being most suitable for Kolbe electrolysis (order of activity Li+<Na+<K+~Cs+). The trend was observed irrespectively of the electrolyte conditions throughout the entire pH range at low current densities (25 mA/cm2), i.e. at pH 3 where OER is dominating, pH 5 where OER transitioned to Kolbe electrolysis and pH 9 where Hofer Moest reaction occurs. With increasing current densities (>50 mA/cm2), the influence of cations on electrooxidation diminishes showing the limitations of the effect of non-covalent interactions.
To confirm the surface coverage and transition of OER to Kolbe reaction with increasing potential, we probed reaction selectivity in the inflection zone potential regime by means of RRDE. The analysis confirmed that the OER is suppressed completely in the presence of K+ cations after reaching potentials of ~2.5VRHE (inflection zone), while for Li+, OER still proceeds as confirmed by the ORR reaction at the ring electrode. Because surface coverage reflects the high activity of Kolbe electrolysis, we confirmed that the smaller cations interfere more strongly with the electrode surface adsorbed oxygenates due to strong non-covalent interaction and thus affecting the reaction.

References

F. J. Holzhäuser, J. B. Mensah, and R. Palkovits, Green Chem., 22, 286–301 (2020).

C. Stang and F. Harnisch, ChemSusChem, 9, 50–60 (2016).

T. Ashraf, A. P. Rodriguez, B. Mei, and G. Mul, Faraday Discuss. (2023)

H. J. Schäfer, in Comprehensive Organic Synthesis, B. M. Trost and I. Fleming, Editors, p. 633–658, Pergamon, Oxford (1991)

K. Silambarasan, J. Joseph, and S. Mayavan, Applied Surface Science, 489, 149–153 (2019).

D. Strmcnik et al., Nature Chem, 1, 466–472 (2009).

C. Han et al., ACS Appl. Mater. Interfaces, 14, 5318–5327 (2022).

B. A. F. Previdello, E. G. Machado, and H. Varela, RSC Advances, 4, 15271–15275 (2014).

Figure 1
Towards Zero Waste Recovery of Li-Ion Battery
Authors: He Ze 
Published: February 2024

The proliferation of lithium-ion batteries (LIBs) has prompted a critical exploration of sustainable waste management strategies within the battery life cycle. This abstract focuses on waste materials generated during LIB recycling, specifically emphasizing waste water, including the presence of lithium ions, which is most generated at delamination and leaching process, and waste graphite.
Waste water, a significant outcome of LIB recycling, often contains valuable lithium ions. Efficient extraction and purification of lithium ions from waste water not only recovers a precious resource but also mitigates the ecological consequences of improper disposal. Advanced methodologies such as solvent extraction, hydrometallurgy and membrane filtration demonstrate promising avenues for selectively recovering lithium ions from waste water streams.
Furthermore, addressing the disposal of waste graphite electrodes presents an imperative challenge. Graphite, a cornerstone of LIBs, holds substantial potential for reclamation. Innovations encompassing thermal and chemical processes have been explored for graphite extraction from discarded electrodes. In this study, the recycled graphite after heat treatment direct reuse in batteries is performed. This approach aligns with the principles of a circular economy, promoting resource efficiency and reducing the dependence on primary graphite sources.
In conclusion, the recycling of lithium-ion batteries generates waste materials, with a particular focus on waste water enriched with lithium ions and waste graphite electrodes. Confronting these challenges mandates the implementation of advanced recycling techniques. By harnessing valuable materials and alleviating environmental pressures, the LIB recycling sector can lead the transition toward sustainable practices, significantly contributing to a greener and more resource-conscious energy landscape.
(Invited) Novel Surface Reactions in Low-Temperature Regime for High-Aspect-Ratio Dielectric Etching
Authors: Honda Masanobu , Suda Ryutaro , Tanaka Koki , Yokoi Masahiko , Tomura Maju , Kihara Yoshihide 
Published: February 2024

The most critical issue to achieve High-Aspect-Ratio (HAR) dielectric etching is the transport of both radicals and ions to the bottom of a feature [1]. Current HAR dielectric etching uses fluorocarbon and hydrofluorocarbon gases combined with high applied bias power. However, the etch rate drastically decreases at high depth due to the decline of radicals being supplied to the etch front. Alternative methods have long been required to solve this problem. To address the radical transport issue, we propose adopting a novel precursor with low molecular weight to enhance Knudsen transport. In addition, cryogenic temperature regimes are also known to enhance etch rates [2][3] but have not yet been implemented for HAR dielectric etching.
In this work we evaluated a novel precursor in cryogenic temperature regime for HAR dielectric etching. For the first time, we demonstrate a synergy effect between cryogenic temperature and this novel precursor by successfully developing an innovative HAR dielectric etch process. We confirmed that this process is capable of etching beyond a ten-micron depth for a 3D-NAND channel hole with a hundred nanometer critical dimension in diameter, thus an aspect ratio of over one hundred to one. The key to enabling high etch rate is strongly correlated with the adsorption of the precursor on the surface, which is enhanced at cryogenic temperature. Detailed surface adsorption reaction mechanisms will be described in the conference.
This new process not only enables higher etch rate, higher selectivity and higher aspect ratio etching capability, but also significantly shortens the process time with 84% carbon footprint reduction of greenhouse gas emissions.
[1] K. Ishikawa, et al., Jpn. J. Appl. Phys. Vol. 57, No. 6S2, 06JA01, (2018).
[2] T. Ohiwa, et al., Jpn. J. Appl. Phys. Vol.31, p.405, (1992).
[3] R Dussart, et al., J. Phys. D: 47, 123001, (2014).
(Invited) Nanostructured Solid State Battery Architectures Enabled by Atomic Layer Deposition
Authors: Kozen Alexander C 
Published: February 2024

Solid state batteries (SSBs) are considered the most promising next-generation energy storage technology both due to their increased safety over conventional wet Li-ion cells and their ability to fabricate novel architectures with simultaneous high energy and power density. However, the ionic conductivities of many solid electrolyte materials are orders of magnitude lower than liquid carbonate-based electrolytes. In order to offer SSBs with competitive charge/discharge rates, SSB active layers need to be thin (for fast ion diffusion) but have a large surface area (to enable large ion flux from anode to cathode). These geometric constraints establish the need for 3D electrode (and solid electrolyte) structures for a high performance battery architecture. Atomic layer deposition (ALD) is ideally suited to fabricate such devices due to its highly conformal nature and Angstrom-scale thickness control, however many challenges remain with materials fabrication and process integration.
I will discuss development of both plasma-enhanced ALD (PEALD) and thermal ALD processes for the Li, Na, and K alkali polyphosphazene (A*PON) electrolytes1,2,3,4. The PEALD A*PON processes, by virtue of their 4-precursor synthesis route, allow some degree of chemical composition tuning. The thermal A*PON processes, unlike their PEALD counterparts, have a predetermined P-N ratio fixed by use of the precursors, however there is a tradeoff between the low temperature deposition enabled using plasma-based A*PON processes, and the conformality offered using the thermal A*PON processes. I will discuss and compare the reaction mechanisms and growth behavior among the entire family of A*PON solid electrolyte thin films, as well as discuss the integration challenges on the path to developing all-ALD planar and 3D SSBs.

Pearse, A.; Schmitt, T.; Sahadeo, E.; Stewart, D. M.; Kozen, A.; Gerasopoulos, K.; Talin, A. A.; Lee, S. B.; Rubloff, G. W.; Gregorczyk, K. E., Three-Dimensional Solid-State Lithium-Ion Batteries Fabricated by Conformal Vapor-Phase Chemistry. ACS Nano
2018,
12 (5), 4286-4294.

Pearse, A. J.; Schmitt, T. E.; Fuller, E. J.; El-Gabaly, F.; Lin, C.-F.; Gerasopoulos, K.; Kozen, A. C.; Talin, A. A.; Rubloff, G.; Gregorczyk, K. E., Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte. Chemistry of Materials
2017,
29 (8), 3740-3753.

Nuwayhid, R. B.; Jarry, A.; Rubloff, G. W.; Gregorczyk, K. E., Atomic Layer Deposition of Sodium Phosphorus Oxynitride: A Conformal Solid-State Sodium-Ion Conductor. ACS Applied Materials & Interfaces
2020,
12 (19), 21641-21650.

Kozen, A. C.; Pearse, A. J.; Lin, C-F.; Noked, M.; Rubloff, G. W.; Atomic Layer Deposition of the Solid Electrolyte LiPON. Chemistry of Materials
2015,
27 (15), 5324-5331.