bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stabilizing LATP Electrolyte Interface of All-Solid-State Lithium Ion Batteries Consisting of High-Voltage Cathode
Authors: Kang DongJae , Lim Hyung-Tae 
Published: November 2022

NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP) solid electrolyte has been investigated because of its stability in the air and water and wide electrochemical window, which make it a suitable electrolyte material to be used with a high-voltage cathode material. However, LATP solid electrolyte has interfacial problems, as in LiCoO2/LATP results in a limited contact area and Li/LATP suffers from structural collapse due to side reactions.
In the present study, we inserted PEO polymer electrolyte to suppress the Li/LATP interface side reactions and mitigate the LiCoO2/LATP interfacial resistance. We prepared symmetric & full cells with PEO coated on both sides of electrolyte. The symmetric cell consisted of Li/PEO/LATP/PEO/Li and full cell consisted of Li/PEO/LATP/PEO/LiCoO2. The symmetric cell exhibited stable cycling behavior at current density 0.1mA/cm2 for 2000h at 60℃. The full cell charge capacity showed 151.71mAh/g in voltage range of 3.0~4.2V at 60℃ at 0.1C rate. Therefore, PEO protecting layer is effective for stable cycling performance.

Keyword:

All-solid-state Batteries, LATP Solid Electrolyte, Li/LATP Interface, LiCoO2/LATP Interface, PEO polymer electrolyte
Compact Sulfurized-Polyacrylonitrile/Graphene Composite Cathode for High-Energy and Long-Life Li-S Batteries
Authors: Kim Hun , Choi Ha-Neul , Jeong Kyung-Min , Sun Yang-Kook 
Published: November 2022

Next-generation batteries have been in the spotlight to meet the demand for batteries with higher energy densities than commercial lithium-ion batteries. Among them, lithium-sulfur batteries have been actively investigated owing to their attractive features; 1) Ultrahigh energy density, 2) Low cost of sulfur. Herein, we propose a compact, high-performance, 2D sulfurized-polyacrylonitrile/graphene (2D-SPAN/G) cathode for practical Li–S batteries. A 2D-SPAN/G cathode with a high active-mass (sulfur) loading of 10 mg cm−2 is successfully prepared via high-pressure pelletization. In the 2D-SPAN/G cathode, graphene nanosheets function as a robust and conductive scaffold, which uniformly encapsulates SPAN nanoparticles, providing structural integrity and enabling the high electrochemical utilization of sulfur. Combined with the stabilized lithium metal anode by using a modified electrolyte (consisting of 1 M LiPF6 and 0.05 M LiDFOB in EMC:FEC (3:1 (v/v))), and a 2D-SPAN/G cathode delivers a high areal capacity of 11 mAh cm−2 and demonstrats outstanding cycling stability over 300 cycles at a high current density of 4 mA cm−2. Moreover, the excellent electrochemical performance of a scaled-up, pouch-type Li–S battery featuring a 2D-SPAN/G cathode demonstrats the viability of the proposed cathode. The reversibility of the Li+-ion storage mechanism of the 2D-SPAN/G cathode is confirmed using operando Raman spectroscopy.

Reference
s
:

[1] J.-Y. Hwang, S.-J. Park, C. S. Yoon and Y.-K. Sun, Energy Environ. Sci., 2019, 12, 2174–2184.
[2] H. Kim, S. Bang, K.-J. Min, Y.-G. Ham, S.-J. Park and Y.-K. Sun, ACS Appl. Mater. Interfaces, 2021, 13, 39435–39445.
[3] H. M. Kim, J.-Y. Hwang, D. Aurbach and Y.-K. Sun, J. Phys. Chem. Lett., 2017, 8, 5331–5337.
Functional Ionomer Gradients in Anode Catalyst Layers for Low Temperature PEM Water Electrolysis
Authors: Gollasch Marius , Harms Corinna , Wark Michael 
Published: November 2022

Water electrolysis is a crucial technology for large-scale hydrogen generation, that is required for the transition to a fossil fuel-free energy system. Even though water electrolysis systems are already deployed in a limited capacity, the technology is largely constrained to liquid alkaline electrolysis. Proton exchange membrane (PEM) electrolysis could pose an alternative but it is still hindered by high investment costs, in-part due to its reliance on scarce noble-metal catalysts. Alternative structural designs of the anode catalyst layer (CL) could reduce Iridium loading of the whole system and thus accelerate its wide-spread application. In fuel cell research, it was already reported that a multi-layer design with varied ionomer content enhances performance of the CL and in-turn lowers required catalyst loading.[1,2,3]
In this study, a gradient design for ionomer content is employed for anode CLs for the application in PEM water electrolysis. CLs are coated in a stacked multi-layer design via ultrasonic spray coating of Iridium/Nafion® suspensions. The target ionomer loadings (10 and 30 wt.%) are confirmed by a combination of thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The coating process yields homogenously loaded reference CLs as well as through-plane graded CLs with the desired ionomer loading. Additionally, scanning electron microscopy (SEM) in conjunction with energy dispersive spectroscopy (EDS) shows equal CL thickness across all ionomer loadings and spatially differentiated Nafion® content throughout the CLs thickness. Electrochemical characterizations are carried out in an electrolysis-adapted gas diffusion electrode (GDE) half-cell setup to allow for quick examination and prototyping of produced layers. Differences in electrochemical performance of these layers can be observed with one gradient design CL showing reduced overpotential across all current densities compared to the homogenous CLs. In-particular a high ionomer loading near the membrane improves performance, most likely due to increased proton conduction to the membrane and higher available pore volume near the porous transport layer.
Further analysis is performed on electrochemical studies to deepen the understanding of the role of ionomer in anodic PEM water electrolysis CLs. Particularly, the investigation of protonic and electric conductivity through the CL is of interest, because this parameter is most influenced by ionomer loading.[4]
References:
[1] Y. Wang, T. Liu, H. Sun, H. Wie, F. Yuanzhi, S. Wang, Electrochimica Acta
2020, 353, 136791.
[2] R. Roshandel, F. Ahmadi, Renewable Energy
2013, 50, 921-931.
[3] K.-H. Kim, H.-J. Kim, K.-Y. Lee, J.H. Jang, S.-Y. Lee, E. Cho, I.H. Oh, T.H. Lim, International Journal of Hydrogen Energy
2008, 33, 2783-2789.
[4] M. Mandal, M. Moore, M. Secanell, ACS Applied Materials & Interfaces
2020, 13, 49549-49562.

Figure 1
Understanding Gas Permeation during High Pressure Operation of PEM Water Electrolyzers
Authors: Khedekar Kaustubh , Van Pelt Christopher Evan , Gebhardt Ryan , Zenyuk Iryna V. , Bender Guido , Mukundan Rangachary , Park Andrew M , Borup Rod L. , Komini Babu Siddharth 
Published: November 2022

Governments and industries across the world have initiated implementation of clean hydrogen (H2) to achieve zero emissions, yet significant challenges remain for large scale adoption. With the decreasing renewable electricity cost PEM water electrolyzers (PEMWEs) show significant potential for at scale deployment due to their high faradaic efficiency and high operating current density. To reduce the per kilogram price of hydrogen and increase the overall energy efficiency, PEMWEs need to be operated at high differential pressures (30 to 50 bar) to eliminate the need for compression during storage and transportation1. To achieve high faradaic efficiency, thinner membranes are required to reduce voltage losses within the cell. However, thinner membranes exhibit a higher gas permeation rate which leads to increased crossover of hydrogen from the cathode through the membrane to the anode. Such increased crossover of H2 not only reduces the efficiency but can also result in flammable gas mixtures (lower flammability limit for H2 in O2 is 4 %) as Iridium/Iridium oxide (anode catalyst) is inefficient in oxidizing H2
1. The addition of a gas recombination catalyst (GRC) to the membrane is an useful strategy to oxidize permeating H2 and minimize the H2:O2 ratio at the anode.
In this study, a high pressure (up to 30 bar) electrolyzer setup is coupled with online gas chromatography-mass spectrometry to understand the H2 gas permeation in membranes as a function of H2 partial pressure and operating current density (simulated by varying the flow rates) as shown in Figure 1
. Effect of the GRC, its loading, and its location on the H2 permeation will be elucidated. Differences induced by the addition of anode and cathode catalyst layers on H2 permeation rates will also be presented.
Figure 1. Ex-situ H2 permeation rate at different cathode operating pressure at 80 °C. The anode was maintained at 1 bar of O2 partial pressure

Acknowledgement

This research is supported by the U.S. Department of Energy (DOE) through the Hydrogen and Fuel Cell Technologies Office, program manager Dave Peterson

Reference

Bernt, M., Schröter, J., Möckl, M. & Gasteiger, H. A. Analysis of Gas Permeation Phenomena in a PEM Water Electrolyzer Operated at High Pressure and High Current Density. J. Electrochem. Soc.
167, 124502 (2020).

Figure 1
(Invited) Progress and Perspective Towards Low-Cost High-Performance Anion Exchange Membrane Water Electrolysis
Authors: Strasser Derek James , Pupucevski Max , Macauley Natalia , Lattimer Judith , Zhong Sichen , Xu Hui 
Published: November 2022

Hydrogen is at the forefront of clean energy use and storage in the goal to drastically reduce anthropogenic carbon dioxide and combat global climate change. However, hydrogen production to-date is accomplished via steam methane reforming which, for every ton of hydrogen produced 5.5 tons of CO2 is liberated. One viable technical solution for production of clean hydrogen is water electrolysis. To this end DOE has implemented the Hydrogen Earthshot initiative to cleanly produce hydrogen at 2 $/kg by 2025 and 1 $/kg by 2030.
Of the several commercial water electrolysis technologies available, proton exchange membrane water electrolysis (PEMWE) currently offers the most benefits including operations at low temperature, differential pressure, and high current density (≥3 A/cm2). Commercialization of PEMWE has advanced rapidly despite several significant disadvantages which include the necessity of scarce expensive platinum-group metal (PGM) catalysts, expensive perfluorinated membranes, and significant environmental impacts of perfluorinated alkyl substances (PFAS) used in membrane production. The solution to these challenges is the development of alkaline exchange membrane water electrolysis (AEMWE) which retains the advantageous characteristics of PEMWE without the need for PGM catalysts or perfluorinated membranes.
Here in, we report on our current progress of AEMWEs, which covers PGM-free catalyst development, low-cost and durable AEM development and electrode design development. From a commercial point of view, given a high-performance durable membrane, manufacturing MEAs is a critical next step toward commercialization. Therefore, development of an AEM with accessible thermal transitions prior to the onset of quaternary ammonium degradation is key to enabling proven MEA fabrication techniques such as hot-pressing and decal transfer of electrodes. Through a novel synthetic approach, we will describe the preparation of functionalized copolymers and terpolymers containing latent cross-linking functionality. Ultimately, we will demonstrate the manufacturability of MEAs from our PGM-free catalysts and membrane materials employing hot-pressing and decal transfer of electrodes along with single cell evaluations. We will also discuss factors that affect the degradation of AEMWEs and solutions to address these challenges.
(Digital Presentation) Interfacial Durability of Anion Exchange Membrane Water Electrolyzers (AEMWEs)
Authors: Maxwell Derrick , Kendrick Ian , Mukerjee Sanjeev 
Published: November 2022

There is a growing industrial appeal of anion exchange membrane water electrolyzers (AEMWEs) to produce hydrogen. This is spurred by the recent advancements in high current density operation capability with relatively low overvoltage performance. Cost reduction has been pursued by reducing the reliance on expensive platinum group metal (PGM) catalysts while still achieving long-term, continuous operation conditions most relevant to the industry: high current densities above 2 A/cm2 while retaining overvoltage performance so that overall cell potential is less than 2V.
Along with a selection of appropriate PGM-free catalysts, other approaches exist that drive down the associated cost to produce hydrogen from water splitting. Sources of water are extended to brackish and even seawater to further drive down costs due to the removal of costly water purification requirements. The introduction of salt to the water source may improve overvoltage performance in an AEMWE by raising electrolyte conductivity, however, it may also lead to some unknown instability within more severe high current operating conditions. The challenge remains that AEMWE durability testing is not standardized, and more minute interfacial degradation mechanisms between ionomer, catalyst, membrane, and electrolyte are not well characterized for many industrially relevant materials. When approaching AEMWE performance improvements with PGM-free and variable electrolyte content in water solution sources, the long-term performance needs to be demonstrated in a stable and reliable manner.
A series of in-situ Raman experiments are presented in coordination with ex-situ spectroscopic and physical analysis of components in PGM-free AEMWEs that are expected to contribute to overall degradation of electrolyzer performance. Interfacial durability improvements are sought by providing insight into the main sources of failure during high current and long-term operations. Electrochemical testing protocols are also developed and presented in order to seek standardization of testing procedures. In-line gas chromatography (GC) analysis is also presented in tandem with other analytical methods to confirm product gas purity and corroborate hypotheses on possible degradation mechanisms.
(Digital Presentation) Electrode and Electrolyte Materials for Thin Film Microbatteries
Authors: O'Donoghue Aaron , Mc Grath Louise , Povey Ian , Rohan James F. , Shine Michael 
Published: November 2022

Electrode and Electrolyte Materials for Thin Film Microbatteries,

Aaron O’Donoghue, Louise McGrath, Ian Povey and James Rohan

In this work we assess the electrochemical performance of electrodeposited, binder-free V2O5 thin films with Li metal anodes in liquid and polymer gel electrolytes based on a pyrrolidinium based ionic liquid (C4mpyrTFSI). Coulombic efficiencies >99%, with electrode capacities >120 mAh g-1 are obtained in cyclic voltammetry analysis of crystalline V2O5 with C4mpyr-based Ionic liquid (IL) electrolytes. A polymer gel electrolyte suited to layer by layer microbattery fabrication was synthesised and tested with the crystalline V2O5 and gave large electrode capacities at a relatively high rate (110 mAh g-1 at 2 C) similar to those obtained in liquid electrolytes. Stable long-term cycling (up to 400 cycles) is obtained with Li metal anodes without capacity fade or short circuits developing in either the VC containing IL or the polymer gel analogue. In addition, no V2O5 deterioration is observed with the polymer gel electrolyte as the capacity recovered to ~125 mAh g-1 after cycling at 5 C.
Furthermore, we assess surface modification of V2O5 by depositing 3nm Al2O3 via ALD which has been shown to improve the charge-discharge kinetics of oxide electrode materials. Coulombic efficiencies >99%, with peak electrode capacities >120 mAh g-1 are obtained and long-term cycling stabilities up to 625 cycles.
1) L. M. McGrath and J. F. Rohan, Batteries & Supercaps, 4 (2021) 485 – 492, High rate lithium ion cycling in electrodeposited binder-free thin film vanadium oxide cathodes with lithium metal anodes in ionic liquid and polymer gel analogue electrolytes.
2) L. M. McGrath and J. F. Rohan, Molecules, (2020), 25. 6002, Pyrrolidinium containing ionic liquid electrolytes for Li-based batteries.
3) T. Teranishi, Y. Yoshikawa, M. Yoneda, A. Kishimoto, J. Halpin, S. O’Brien, M. Modreanu and I. M. Povey, (2018), ACS Applied Energy Materials, 1(7), pp. 3277-3282, Aluminum Interdiffusion into LiCoO2 Using Atomic Layer Deposition for High Rate Lithium Ion Batteries.

Figure 1: Charge/Discharge capacity of 3nm Al2O3 coated V2O5 vs Li foil in 1M LiPF6 in EC:DEC (1:1)

Figure 1
Lithium Substitution in P3-Structured Copper-Based Cathodes for Sodium-Ion Batteries
Authors: Ronne Arthur , Liu Jue , Yang Xiao-Qing , Chen-Wiegart Yu-chen Karen , Hu Enyuan 
Published: November 2022

Sodium-ion batteries promise low-cost energy storage for the grid and electric vehicles, building upon the established “rocking-chair” Li-ion design, while benefitting from the natural abundance of sodium and the ability to utilize iron or copper redox reactions to further reduce the material cost. Nonetheless, Na-ion adoption has been hindered due to low energy density and large structural changes leading to poor long-term cyclability. It has been recently shown that additional reversible capacity can be obtained through oxygen redox with low voltage hysteresis in selected Na-ion layered oxide cathodes. However, the mechanisms and the intermediate species that enable this reversible oxygen redox are highly debated and not fully understood. Here we focus on several P3-structured sodium-deficient NaxY1/3Mn2/3O2 cathodes, where Y can be Cu or derivatives with partial lithium substitution, to elucidate how lithium substitution influences both the redox mechanism and the structural evolution during electrochemical cycling. Our results show a small amount (~7%) of lithium substitution can change the reaction pathway from a two-phase reaction to a solid solution mechanism, increasing stability and capacity retention. A multimodal characterization approach combining synchrotron-based X-ray spectroscopy, microscopy, and scattering techniques along with nuclear magnetic resonance spectroscopy, provides insights into the redox mechanisms, chemical species distribution, structural evolution, and phase transitions during electrochemical cycling.
Acknowledgment: The work at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program under contract DE-SC0012704. This research used resources of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704.
Driving Force behind the Amorphization in the Crystalline Cathode Structures during Alkali Metal Ion Intercalation for Electrochemical Energy Storage
Authors: Ozdogru Bertan , Capraz Omer Ozgur Özgür 
Published: November 2022

Development of cathode structures suitable for Na-ion and K-ion batteries is still one of the major challenges on the way to the design of next-generation alkali metal-ion batteries. Although Li, Na and K belong to the same alkali metal group with a single charge in their cation form, intercalation of Na+ and K+ ions in electrodes is difficult since ionic radii of Na+ (0.98 Å) and K+ (1.38 Å) are larger than that of Li+ (0.69Å). Intercalation of alkali metal ions results in volumetric expansions in the electrode structure. Even modest expansions in brittle cathodes can cause particle fracturing in a larger crystalline-size scale. Intercalation of larger ions can cause structural collapse and amorphization induced by continuous accumulation of strains and distortions. However, the lack of understanding behind the amorphization mechanisms in the crystalline electrodes upon ion intercalation materials hinders the development of electrode structures suitable for these large ions.
In the first part of the talk, we will first report the utilization of in situ digital image correlation and in-operando X-ray diffraction (XRD) techniques to probe dynamic changes in the amorphous phase of iron phosphate during potassium intercalation1. A new experimental approach allows to monitor dynamic physical and structural changes in the amorphous phase of the electrodes. This method offers new insights to study mechanics of ion intercalation in the amorphous nanostructures.
In the second part of the talk, we will discuss the electrochemical and mechanical response of the iron phosphate cathodes upon Li, Na and K ion intercalation. Strain evolution during Li and Na intercalation results in more linear dependence on the state of charge / discharge. However, strains generated in the electrode shows nonlinear behavior during insertion / extraction of K ions. Strain rate calculations showed that K ion intercalation results in a progressive increase in the strain rate, whereas Li and Na intercalation induce nearly constant strain rates2. Our results shows that strain rates are critical factor for the amorphization of the crystalline structure, rather than the absolute value of electrochemical strains. These observations provide a fundamental insight into the impact of alkali ions on the redox chemistry and associated chemomechanical deformations.
Acknowledgement: This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (Award number DE-SC0021251).
References:
1) B. Ozdogru et al, Nano Letters, 21, 18, 7579–7586, 2021.
2) B. Ozdogru et. al, Electrochemical Science Advances, e2100106, 2021.
(Invited, Digital Presentation) Design of New Cathodes for Sodium-Ion Batteries Harnessing Anionic Redox Activity: Two Case Studies
Authors: Vanam Sai Pranav , Barpanda Prabeer 
Published: November 2022

Sodium-ion batteries (SIBs) are widely pursued as pragmatic alternative to the Li-ion battery technology having close operational similarity along with natural resource abundance. In this sector, apart from classical cationic redox-based cathodes, various new cathodes have been unveiled based on anionic (oxygen) redox activity. In this work, we will showcase two such case studies of novel cathode composition for SIBs exploiting anionic redox activity.
(1) P2-type manganese-rich layered oxides offers high capacity along with fast rate kinetics. To improve their electrochemical properties, reduce voltage decay upon cycling and to mitigate irreversible phase transitions, cation doping or hybrid composite integrations can be explored. We have tested a unique Mn-rich layer-spinel composite, Na0.7(Li1/18Mn11/18Ni3/18Fe2/181
/18)O2–xNa2MoO4, leading to a synergistic effect of layered P2 and spinel phases. This layer/spinel biphasic composite was stabilised through Mo doping and its electrochemical activity was studied at different voltage windows. Upon cycling between 1.5–4.5 V, this Mo-based composite exhibited a high specific capacity of 183 mAh.g-1 involving both cationic and anionic (O2-/O2
n-) redox activity. The structural evolution during (dis)charge was studied by ex-situ X-ray diffraction and cyclic voltammetry. It is observed that mitigating P2-P2´´ phase transition at higher voltage is crucial to improve the electrochemical performance, cycling stability and reduce the voltage hysteresis. The structural and electrochemical properties of this new composite cathode will be described (Fig. a) (manuscript submitted).
(2) The second part will dwell on anionic redox activity of Na-based mixed-metal oxide cathode [Na0.7Mn0.6Ni0.3Co0.1O2]. Combining cationic and anionic redox activity, it exhibited a reversible capacity of 120 mAh/g with anionic redox activity centered around 4.3 V (Fig. b). The underlying redox mechanism has been investigated using in-situ XRD and Raman spectroscopy showing peroxo bond formation (Fig. c). The structural and electrochemical properties of this new cathode composition will be explained (manuscript submitted).

Figure 1