bluuebunny/crossref_metadata_2025_split huggingface dataset:
Quantitative Evaluation of the Low Temperature Discharge Performance of Li-Ion Batteries Using Electrochemical Impedance Spectroscopy
Authors: Brown David Emory , McCloskey Bryan D. 
Published: July 2022

To promote further adoption of electric vehicles (EVs)—as well as to improve the performance of other battery-powered technologies such as phones, laptops, and drones—Li-ion battery (LIB) low temperature performance needs to be significantly improved. At temperatures below 0oC, LIB discharge performance drops drastically below room temperature performance; for example, at -20oC, the LIB C/3 discharge capacity is less than 70% of its 30oC capacity. Significant research efforts are underway to quantify the dominant loss processes in LIBs discharged at low temperatures.
In this work, we use operando impedance spectroscopy during LIB discharge to quantify loss processes and to inform rational electrode and electrolyte engineering to maximize low temperature performance. We show that the graphite charge transfer resistance is the dominant loss process at low temperatures. We also demonstrate that inclusion of 𝛾-butyrolactone (GBL), a low melting point solvent that has similar structure to ethylene carbonate (EC), into the electrolyte as a co-solvent with EC decreases the resistances at the NMC positive electrode during low temperature operation, but it leads to substantial resistance increases at the graphite negative electrode when compared to a similar electrolyte with no GBL added. We discuss physical explanations for these resistance behaviors. Lastly, we use impedance spectroscopy to develop a coupled ion-electron transfer kinetic model to quantifiably compare the low temperature performance of different LIB chemistries. These findings will enable the development of significantly improved LIB discharge performance at low temperatures, paving the way for wider use and adoption of important LIB-powered devices, such as EVs.
Local-Structure Analysis of Li Oxy-Sulfide Glass-Ceramic Solid Electrolytes
Authors: Zimmermanns Ramon , Luo Xianlin , Knapp Michael , Hansen Anna-Lena , Indris Sylvio , Ehrenberg Helmut 
Published: July 2022

In the global quest to tackle climate change and the promotion of sustainable energy sources, energy storage has become an important aspect and consequently has attracted great research attention. Solid state batteries promise increased energy density and safety in comparison to current commercial Li-ion batteries[1]. Fast ion conducting solid electrolyte materials are an essential part of solid-state batteries. The study of suitable materials and the understanding of the conduction mechanisms is therefore of high importance.
Sulfide and thiophosphate glasses have been identified as promising candidates as fast ion conducting materials and great progress has been made since the first studies in 1980[2]. One drawback of these materials is their sensitivity against humidity and instability on exposure to air. Recently, it was demonstrated that the doping of thiophosphate glasses with oxygen has a positive effect on the ion conductivity[2]. Furthermore, an improvement of the chemical and physical stability of these doped glasses could be achieved. The combination of these two effects renders oxygen doping a promising strategy. However, very little is known so far about the local structure of the doped glasses and glass ceramics, yet this information is crucial to enable purposeful development and further improvement of these materials.
Hence, we have studied the local structure of oxy-sulfide glasses as well as their structural evolution and crystallization behavior with increasing temperature. Additionally, the influence of the starting materials was evaluated by comparing materials from two different set of starting materials using the same synthesis route. Oxy-sulfide glasses of the composition Li3POxS4-x with 0 ≤ x ≤ 1.2 were synthesized by ball milling appropriate amounts of either Li2O, Li2S and P2S5, or Li3PS4 and Li3PO4. Temperature dependent x-ray powder diffraction and pair distribution function (PDF) analysis, supported by Raman spectroscopy and other characterization techniques, was then used to identify crystal phases and structural moieties. Subsequently, impedance measurements were carried out to be able to link microstructure to ionic conductivity.
[1] Tan, D.H.S., Banerjee, A., Chen, Z. et al. From nanoscale interface characterization to sustainable energy storage using all-solid-state batteries. Nat. Nanotechnol. 15, 170–180 (2020). https://doi.org/10.1038/s41565-020-0657-x

[2] Martin, S.W. Chapter 14: Glass and Glass-Ceramic Sulfide and Oxy-Sulfide Solid Electrolytes. Handbook of Solid State Batteries, pp. 433-501 (2015) https://doi.org/10.1142/9789814651905_0014

Figure 1
Pseudo-Two-Dimensional Modeling of Lithium-Ion Conversion Cathode Materials
Authors: Horner Jeffrey Scott , Whang Grace , Kolesnichenko Igor V. , Dunn Bruce S. , Lambert Timothy N. , Roberts Scott A. 
Published: July 2022

Conversion cathode materials are an intriguing next-generation chemistry for lithium-ion batteries due to their high theoretical capacity. Nevertheless, there are various practical issues inhibiting current use in consumer products including limited rechargeability due to capacity fade and poor performance at fast cycling rates. Partially responsible for these issues is the current lack of understanding of leading loss mechanisms for conversion cathode materials as the changing composition of the electrode makes it difficult to isolate and eradicate cell limitations. Electrochemical models are typically used in combination with experiments to improve understanding of cell performance and limitations. However, in comparison to intercalation cathode materials, fewer modeling studies have been conducted for conversion cathode materials. As such, a robust and efficient model for lithium-ion conversion cathode electrochemistry is desirable to optimize these materials for practical use.
Here, we present a pseudo-two-dimensional model for conversion cathode materials implemented using the open-source Python Battery Mathematical Modelling (PyBaMM) software. We apply the model to FeS2 – an intriguing material due to its abundance and high theoretical capacity. Upon discharge, FeS2 first undergoes an intercalation reaction followed by a conversion reaction with lithium to produce Li2S and Fe. The model is based on a polydisperse, core-shell approach for active material particles where the intercalated FeS2 core converts to a shell of Li2S, and two distinct sources for the current associated with the two separate reactions are enabled at the reaction surface. Upon initiation of the conversion reaction, an additional parameter representing the thickness of the converted shell material is tracked and used to incorporate ionic and electronic transport losses through this material. By comparing the model with experimental discharge data, we identify the leading loss mechanisms as poor solid-state diffusion during the intercalation reaction and poor electronic conductivity through the converted shell during the conversion reaction. Our analysis helps to guide design and optimization of FeS2 cathodes, and the adaptability the model encourages its use for other conversion cathode materials.
Supported by the Laboratory Directed Research and Development program at Sandia National Laboratories, a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525.
Analysis of the Interphase Formation of Thiophosphate Solid Electrolytes and the Lithium Metal Anode in Solid-State Batteries
Authors: Riegger Luise M. , Sann Joachim , Richter Felix H. , Janek Jürgen 
Published: July 2022

Due to their high ionic conductivities and better safety, thiophosphate solid electrolytes (SEs) such as Li6PS5Cl or Li7SiPS8 are of interest for applications in solid-state batteries (SSBs). However, drawbacks such as their inherent reduction instability, which impede their application with a lithium metal anode (LMA) [1] as well as low gravimetric and volumetric energy densities of the resulting full cells [2] still have to be overcome.
If the decomposition products of SEs formed upon contact with lithium metal are sufficiently electronically conductive, the decomposition layer forms a so-called mixed conducting interphase (MCI). A (semi)metal dispersed in the MCI should decrease the internal resistance and lead to short circuits [3]. However, this is not the case for all metal ion containing SEs [4]. For example, the resistance of a Li|Li7SiPS8|Li symmetric cell constantly increases. Thus, knowledge about the composition of the interphase between lithium metal and SEs as well as the resistance evolution of a cell containing the respective SE is necessary.
We report our latest findings of the stability of several thiophosphate SEs in contact with lithium metal. We show the kinetics of the heterogeneous solid-state reaction and the chemical composition of the resulting interphase layer. Impedance spectroscopy measurements were conducted to investigate the temporal evolution of the interphase resistance between the lithium metal anode and the SE. In situ-sputter-deposition of lithium metal onto the surface of the SE pellets and subsequent X-ray photoelectron spectroscopy (XPS) measurements are performed to study the chemical composition upon contact. Multiple repetitions of these steps allow a detailed characterization and identification of the decomposition products within the forming interphase. The combined results of our studies allow us to distinguish between the possible interphases of metal ion containing electrolytes and promotes the understanding of the SE stability towards LMAs.

Reference
s
:

[1] X. Li, J. Liang, X. Yang, K. Adair, C. Wang, F. Zhao, X. Sun, Energy Environ. Sci. (2020) 10.1039/C9EE03828K.
[2] P. Braun, C. Uhlmann, M. Weiss, A. Weber, E. Ivers-Tiffée, J. Power Sources 393 (2018) 119-127.
[3] S. Wenzel, T. Leichtweiss, D. Krüger, J. Sann, J. Janek, Solid State Ion. 278 (2015) 98-105.
[4] L. Riegger, R. Schlem, J. Sann, W. Zier, J. Janek, Angew. Chem. (2020) 10.1002/ange.202015238.
Estimating Electrodeposition Properties and Processes: Cu-Ag Alloy at n-Si(001) and Ru Substrates from Acidic Sulfate Bath
Authors: Sun Yunkai , Shao Wenbo , Giurlani Walter , Innocenti Massimo , Zangari Giovanni 
Published: July 2022

A simple method for estimating the composition and duration of the initial stage of alloy electrodeposition is important for deposition process design and the deposit characterization. Analytically or numerically solving the complete diffusion-migration-convection problem based on common simulation methods could be difficulty to be implicated as an ordinary task for designing alloy electrodeposition parameters and electrolytes.
In this work, we have proposed some simple estimations for the initial stage of Cu-Ag alloy electrodeposition, at Si(001) or polycrystalline Ru, regarding (1) the potential-composition curve, (2) the thickness of the initial deposit, and (3) the time interval to reach the steady state deposition, based on the stagnant diffusion layer model. The limiting deposition current is compared with the numerical results from Selman and Newman in 1970s [1]. Meanwhile, composition of the film deposited under limiting current with various electrolyte chemistries is compared with the model suggest by Brenner [2]. Despite the model proposed in this work are highly simplified and not precisely realistic, estimated values show good agreement with the observed values.

Reference:

[1] J.R. Selman, J. Newman, Migration in Supported Electrolyte Solutions with Free Convection, (1971).
[2] A. Brenner, 11 The Role of the Cathode Diffusion Layer in the Electrodeposition of Alloys, in: A. Brenner (Ed.) Electrodeposition of Alloys, Academic Press1963, pp. 307-330.

Disclaimer:

This work has been published at Electrochimica Acta, 403:139695 with title "Estimating electrodeposition properties and processes: Cu-Ag alloy at n-Si(001) and Ru substrates from acidic sulfate bath". Figure attached is chosen from this manuscript.

Figure (a) Observed and estimated composition-potential curve for Cu-Ag electrodeposition system. (b) Film thickness v.s. deposition time, and (c) film thickness v.s. composition of the film, from which Ag-rich initial deposit was observed.

Figure 1
Physicochemical Interplay in Solid Polymer Electrolytes: Benchmarking, Prospects and Limits in High Voltage Batteries
Authors: Kasnatscheew Johannes , Stolz Lukas , Winter Martin 
Published: July 2022

A systematic R&D of solid electrolytes (SEs) requires reasonable benchmark systems for the intra- and interlaboratory comparison and evaluation. Given its abundance, costs, compatibility with Li and a relative simplicity in processing, the poly(ethylene oxide)-based solid electrolyte (PEO-based SE) is a reasonable benchmark SE system for solid-state lithium batteries.(1)
On the basis of recent progress in cell design and methodology,(2-5) the physicochemical properties of PEO-based SE are elaborated as a function of Li salt concentration and related with the performance in LiNi0.6Mn0.2Co0.2O2 (NMC622)||lithium cells. The overall aim is to unravel the apparently complex interplay of relevant parameter and finally to demonstrate the prospects and limits of the SPE benchmark in practical lithium-based batteries.(6)
For instance, despite the decrease of the crystalline phases with a Li salt in a plasticizing manner leading to SE membrane softening, the accompanied increase in amorphous phases enhances the Li+ diffusion coefficient, which can be easily obtained from the analysis of Li||Li cells with the Sand equation. Both, the increased diffusivity of Li+ and the overall amount of charge carriers leads to improved ionic conductivities with higher Li salt concentration, particularly below the melting point (Tm < 60 °C). In terms of anodic behavior, neither SE decomposition nor Al current collector dissolution is visibly affected by the Li salt concentration, revealing a surprisingly high bulk electrolyte stability of 4.6 V vs. Li|Li+ on practical, i.e. composite electrodes; and an Al dissolution tendency as low as in conventional LiPF6/carbonate-based liquid electrolytes. Finally, at an operation temperature below Tm, Li salt concentration is demonstrated to have a direct link with characteristic performance aspects of e.g. NMC622||Li cells.

J. Mindemark, M. J. Lacey, T. Bowden and D. Brandell, Prog. Polym. Sci., 81, 114 (2018).

L. Stolz, G. Homann, M. Winter and J. Kasnatscheew, Materials Advances, 2, 3251 (2021).

G. Homann, L. Stolz, M. Winter and J. Kasnatscheew, iScience, 23, 101225 (2020).

L. Stolz, G. Homann, M. Winter and J. Kasnatscheew, Materials Today, 44, 9 (2021).

G. Homann, L. Stolz, J. Nair, I. C. Laskovic, M. Winter and J. Kasnatscheew, Sci Rep, 10, 4390 (2020).

L. Stolz, S. Röser, G. Homann, M. Winter and J. Kasnatscheew, The Journal of Physical Chemistry C, 125, 18089 (2021).

Figure 1
Non-Fluorinated Diluent Making Localized High-Concentration Electrolyte for Lithium Metal Anode Battery
Authors: Moon Jun-yeob , Kim Dongok , Bekaert Lieven , Song Munsoo , Chung Jinkyu , Lee Danwon , Hubin Annick , Lim Jongwoo 
Published: July 2022

Localized high-concentration electrolyte (LHCE) has been adopted to derive resilient inorganic-rich solid-electrolyte interphase (SEI) layer for lithium-metal anodes (LMA) and increase the ionic conductivity of high-concentration electrolyte (HCE). While the ideal diluent molecules used in LHCE should be miscible in electrolyte system, it should not solvate lithium-ion effectively. To date, systematic investigation to reveal the design rule of diluent molecules remain poorly investigated. In addition, the choice of diluents is largely limited to fluorinated organic molecules which are expensive and environmentally hazardous and unstable at the reductive potential. Because of poor cathodic stability, fluorinated diluents (FDs) have failed to achieve cycle lives longer than 500 cycles in lithium metal half-cell.
Herein, we establish the design rule of diluents for the ideal LHCE, which allows to derive three non-fluorinated diluents (NFDs) systematically. We present that two solvatochromic parameters, HBA basicity (β) and normalized electronic transition energy (ET
N), unravel the generalization rule for the lithium-ion solvation capability and miscibility of diluents. Our design rule discovers three NFDs: anisole, ethoxybenzene, and furan. These NFDs have the unique resonance structures which effectively delocalize the oxygen lone pair electrons and thus enhance non-solvating characteristics, confirmed by the β value and the density functional theory (DFT) calculation. In addition, nuclear magnetic resonance (NMR) spectroscopy studies confirm that our NFDs remains stable and unreacted after long-term cycling. Finally, NFD-containing electrolytes achieve superior cyclability up to 1400 cycles, the record for LHCE to date. The results obtained in this study may pave the way for designing advanced electrolyte for next generation LMA.
Nonflammable Sulfone-Based Electrolytes for Achieving High-Voltage Li-Ion Batteries Using LiNi0.5Mn1.5O4
Cathode Material
Authors: Pham Ngan K. , Truong Tuyen T.T , Le Kha Minh , Huynh Tuyen Thi Kim , Tran Man V. , Le Phung 
Published: July 2022

High voltage Li-ion batteries have been expected a forward technology designed for vehicles, marines and other high power and energy density applications 1–3. Among high voltage cathodes, LiNi0.5Mn1.5O4 is considered a promising cathode to reduce the battery cost as well as environmental hazard issues4,5. However, a high operation potential and Mn dissolution brings the most critical challenges for achieving the long cycle-life of Li-ion cell6,7.
In this study, we report a rational design of nonflammable electrolyte based on LiBF4 and sulfolane (TMS) mixed with a dimethyl carbonate (DMC) as co-solvent to enhance conductivity. Among different molar ratios, the electrolyte LiBF4: TMS: DMC =1:2:1 in mol. exhibited the highest electrochemical stability (~ 6.1 V vs. Li+/Li) and ionic conductivity up to 1.57 mS.cm-1 at 30 oC. Cycling performance of LNMO/Li half-cell and LNMO/graphite full-cell cycled were carried out using the optimized electrolyte. While half-cells LNMO//Li display a high initial capacity of 118 mAh.g-1 and remain 56.48 % of initial value after 100 cycles, a full cell LNMO//Graphite with an areal loading of 1.0 mAh.cm-2 and low N/P ratio (~1.2) exhibited a better cycling stability than the one using commercial electrolyte 1M LiPF6/EC-DMC, 1:1 in vol (with initial capacity of 87 mAh.g-1 and capacity retention of 18% after 100 cycles8).

References

Goodenough JB, Kim Y. Challenges for Rechargeable Li Batteries. Chem Mater. 2010;22(3):587-603.

Etacheri V, Marom R, Elazari R, Salitra G, Aurbach D. Challenges in the development of advanced Li-ion batteries: a review. Energy Environ Sci. 2011;4(9):3243.

Amine K, Kanno R, Tzeng Y. Rechargeable lithium batteries and beyond: Progress, challenges, and future directions. MRS Bull. 2014;39(5):395-401.

Kim J-H, Myung S-T, Sun Y-K. Molten salt synthesis of LiNi0.5Mn1.5O4 spinel for 5 V class cathode material of Li-ion secondary battery. Electrochim Acta. 2004;49(2):219-227.

Patoux S, Daniel L, Bourbon C. High voltage spinel oxides for Li-ion batteries: From the material research to the application. J Power Sources. 2009;189(1):344-352.

Jang DH, Shin YJ, Oh SM. Dissolution of Spinel Oxides and Capacity Losses in 4 V Li / LixMn2O4 Cells. J Electrochem Soc. 1996;143(7):2204-2211.

Du Pasquier A, Blyr A, Courjal P. Mechanism for Limited 55°C Storage Performance of Li1.05Mn1.95 O 4 Electrodes. J Electrochem Soc. 1999;146(2):428-436.

Wang J, Yamada Y, Sodeyama K, Chiang CH, Tateyama Y, Yamada A. Superconcentrated electrolytes for a high-voltage lithium-ion battery. Nat Commun. 2016;7(1):12032.

Acknowledgement

This work is supported by Ho Chi Minh city - Department of Science and Technology (DOST) under grant number 54/2020/HĐ-QPTKHCN.
Investigation of the Redox Activity in Mn-Based Oxyfluorides
Authors: Roy Indrani , Cabana Jordi 
Published: July 2022

Li-ion batteries offer excellent electrochemical performance, are widely used in vehicle electrification and portable devices, and have huge potential for grid storage applications. Their electrochemical behavior relies primarily on transition metal oxide cathodes. In a recent development, Mn has been used in Li-rich cathode materials with a cationic disordered rock-salt (DRX) structure [1,2]. These Mn-based DRX materials are promising candidates for next-generation Li-ion battery cathodes because of their large energy densities and basic favorable features of Mn, such as sustainability. Along with the use of Mn in a DRX structure, substitution of some of the oxygen by fluorine imparts improved cyclability [1-6]. It has been proposed that Li-site distribution played an important role in the initial capacity of these materials and the metal-redox capacity and reversibility was improved by fluorination [5,6]. However, the contribution of the different ions to this improvement has not been fully elucidated. Fluorine and oxygen have different bonding interactions with transition metals, raising the question of how they may comparatively participate in redox compensation. To address this question and determine the role of a mixture of anions in improving the energy density in such cathode materials, we conducted a deep dive into Li2MnO2F as a model cathode material [6]. We interrogated the covalent interaction between the oxygen 2p states, fluorine 2p states, and the transition metal 3d orbitals, and their respective contribution to the charge compensation mechanism using X-ray absorption spectroscopy (XAS). XAS allowed us to resolve the role of both oxygen and fluorine in the electrochemical activity and how covalent interactions are affected by redox, both in extent and in their reversibility.
References:

Gerbrand Ceder et. al. "The Configurational Space of Rocksalt‐Type Oxides for High‐Capacity Lithium Battery Electrodes." Advanced Energy Materials 4, no. 13 (2014): 1400478.

Lee, Jinhyuk et.al. "Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries." science 343, no. 6170 (2014): 519-522.

Freire, Melanie et. al. "A new active Li-Mn–O compound for high energy density Li-ion batteries." Nature materials 15, no. 2 (2016): 173-177.

Reed, J., G. Ceder, and A. Van Der Ven. "Layered-to-spinel phase transition in Li x MnO2." Electrochemical and Solid-State Letters 4, no. 6 (2001): A78.

Lee, Jinhyuk, et al. "Reversible Mn 2+/Mn 4+ double redox in lithium-excess cathode materials." Nature 556, no. 7700 (2018): 185-190. 7/8

Lun, Zhengyan, et al. "Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes." Chem 6, no. 1 (2020): 153-168.