bluuebunny/crossref_metadata_2025 huggingface dataset:
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
(Digital Presentation) Understanding the Chemistry and Microstructure Evolution of Cathodic Interface in All-Solid-State Batteries
Authors: Li Xia , Deng Sixu , Sun Xueliang Andy
Published: July 2022

All-solid-state lithium-ion batteries (SSLIBs) are promising candidates to meet the requirement of electric vehicles due to the intrinsic safety characteristics and high theoretical energy density. A stable cathodic interface is critical for maximizing the performance of SSLIBs. In our study, operando X-ray absorption near-edge spectroscopy (XANES) combined with transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) is employed to investigate the interfacial behavior between the Li-ion cathodes and sulfide solid-state electrolyte. Constructing a uniform interlayer by atomic layer deposition (ALD) is also employed in this study to further investigate the cathodic interface stability. These results provide new insight into the cathodic interface reaction mechanism and highlight the importance of advanced operando characterizations for SSLIBs.
Influence of Acetylation and Polymerization Degree of Chitosan As Green Binder Material for LiMn2O4 Positive Electrodes in Lithium Ion Batteries
Authors: Kuenne Sven , Püttmann Frederik
Published: July 2022

The increasing market of lithium ion batteries within the climate crisis consequently leads to a need of environmentally friendly battery materials and production. Organic solvents, fluorinated binders and toxic transition metals are common components in state-of-the-art batteries. Aqueously processed ecofriendly electrodes are reported showing high electrical performance combined with high work safety and sustainability. In this study, the biopolymer chitosan is investigated electrochemically and mechanically as green binder for positive electrodes utilizing lithium manganese oxide (LiMn2O4; LMO) for the first time. Therefore, chitosans were tailored to a high and low degree of polymerization (DP) and three comparable degrees of acetylation (DA). The systematical comparison of these binder materials reveals insights into the impact of polymer binder properties on the electrochemical performance of positive electrodes. Low DP chitosan show a higher adhesive strength than high DP chitosans or PVdF, while chitosan-based electrodes with DA<16% deliver higher discharge capacities and Coulombic efficiencies in T-type cells than with DA>16% or even with the state-of-the-art binder polyvinylidene difluoride (PVdF). Crosslinking of chitosans with citric acid (CA) further increases discharge capacities up to 80 mAh g-1 at 10C and shows again a superior electrochemical performance with sustainable battery materials.

Figure 1
(Digital Presentation) Insight into the Electrolyte Decomposition Under Abused Testing Protocol Towards Ni-Rich Li-Ion Batteries
Authors: Sawangphruk Montree , Homalamai Kan
Published: July 2022

Nowadays, Li-ion batteries (LIBs) have been gained a lot of attention in the energy storage field since its widely used for many applications. However, the misuse or misoperation of the batteries can generate electrolyte decomposition causing a short life span and safety hazards. Herein, two types of Ni-rich NMC811 i.e., single-crystal and polycrystal were used to study the electrolyte evolution under conventional and abused battery testing protocols. The in-house in situ cells shed light on electrolyte decomposition analyzed by NMR, GC-MS, and ICP, DEMS, and computational calculation. We found that the amount of gas was produced under the system using the polycrystalline NMC811cathode was significantly more than that using the single crystalline NMC811.
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.
Silver Nanoparticles on Vertical Graphene As a Stable Lithium Host for Lithium-Metal Batteries
Authors: Li Wenyue , Lin Xueyan , Fan Zhaoyang
Published: July 2022

The direct use of lithium metal in batteries is jeopardized by the challenging issues related to lithium dendrites or nonuniform lithium deposition, especially in liquid electrolyte and under high current density. Engineering a lithium host that can promote uniform lithium stripping/plating process has attracted tremendous interest to address the challenges. In this study, we design a hierarchical 3D structure, in which edge-oriented graphene (EOG) nanosheets modified carbon nanofiber (CNF) film is used as a scaffold, decorated with Ag nanoparticles (Ag@EOG-CNF), as the lithium host and current collector. Ag nanoparticles not only render the EOG-CNF lithiophilic but also serve as the seeding sites for lithium nucleation to regulate lithium deposition process. In comparison with the previously reported carbon nanofibers or graphene-based lithium hosts, EOG and Ag modification can significantly increase the available surfaces for lithium deposition with reduced local current density. As a result, the Li/Ag@EOG-CNF electrode showed very stable lithium plating/stripping in both symmetric (~25 mV of overpotential within 1000 h of cycling time at the current density of 2 mA cm-2 and capacity of 2 mAh) and asymmetric (Coulombic efficiency maintains above 98.5% within 200 h of cycling time at the current density of 1 mA cm-2 and capacity of 2 mAh) cells.
Anodic Layer Growth on 1050 and 2024 Aluminium Alloys in Presence of Etidronic Acid : Changes in Morphology and Structure
Authors: Jérémy Daval , Moutarlier Virginie , Viennet Rémy , Ricq Laurence , Hihn Jean-Yves
Published: July 2022

Anodic layer growth during anodization is a well-known phenomenon, used to increase the thickness of the natural layer present on the surface of metals for corrosion resistance. In the case of pure aluminum and its alloys, the porous oxide layer leading to a regular structures with nanopores arrangements, which provides interesting corrosion resistance and mechanical performances. The most frequent electrolytes (sulfuric, oxalid or phosphoric acid) induce low current/voltage at direct or pulsed modes to elaborate the oxide layer according to the different electrochemical windows. If the anodic oxide film elaborated in the first moment is soluble into the electrolyte, a porous structure take place with pores oriented perpendicular to the metal surface. The formation of the barrier layer occurs at the interface between the metal and the porous layer, but is thin enough to allow a continuous ionic flow which lead to a continuous film growth.

The present work deals with aluminum anodization in etidronic acid (HEDP) at very high voltages for aluminum 1050 and 2024 alloys. It appears that the oxide layer growth, studied by XRD and SEM pictures of cross section obtained by ionic polishing, differs clearly for the reason that pores formations not only starts from the barrier layer, but also at different locations such as the oxide layer/electrolyte interface. The final result consist in an oxide layer with excellent functional properties.
(Invited) Tracking Metal Electrodeposition Dynamics from Nucleation and Growth of a Single Atom to a Crystalline Nanoparticle
Authors: Hussein Haytham E. M. , Maurer Reinhard J. , Amari Houari , Peters Jonathan J. P. , Meng Lingcong , Beanland Richard , Newton Mark E. , Macpherson Julie V.
Published: July 2022

In electrodeposition the key challenge is to obtain better control over nanostructure morphology. Currently, a lack of understanding exists concerning the initial stages of nucleation and growth, which ultimately impact the physicochemical properties of the resulting entities. Using identical location scanning transmission electron microscopy (STEM), with boron-doped diamond (BDD) serving as both an electron-transparent TEM substrate and electrode, we follow this process, from the formation of an individual metal atom through to a crystalline metal nanoparticle, under potential pulsed conditions. In doing so, we reveal the importance of electrochemically driven atom transport, atom cluster formation, cluster progression to a nanoparticle, and the mechanism by which neighboring particles interact during growth. Such information will help formulate improved nucleation and growth models and promote wider uptake of electrodeposited structures in a wide range of societally important applications. This type of measurement is possible in the TEM because the BDD possesses inherent stability, has an extremely high thermal conductivity, is electron beam transparent, is free from contamination, and is robust enough for multiple deposition and imaging cycles. Moreover, the platform can be operated under conditions such that we have confidence that the dynamic atom events we image are truly due to electrochemically driven deposition and no other factors, such as electron-beam-induced movement.

Figure 1
(Invited) Bare and Modified Cu(111) Electrocatalysts: Interfacial Structure and Reactivity
Authors: Auer Andrea , Bandarenka Aliaksandr S. , Hörmann Nicolas , Andersen Mie , Reuter Karsten , Kunze-Liebhäuser Julia
Published: July 2022

A very important parameter for the electrocatalytic performance of a material is its potential of zero free charge (pzfc). For Cu(111) at pH 13 it was identified at −0.73 VSHE in the apparent double layer region. It shifts by (88±4) mV to more positive potentials per decreasing pH unit.1 At the pzfc, Cu(111) starts to restructure. At higher potentials, full reconstruction and electric field dependent OH adsorption occur, causing a remarkable decrease in the atomic density of the first Cu layer.1 It is this restructuring that enables Cu(111) to efficiently oxidize CO and to reduce water. Therefore, knowledge of the surface structure and the position of the pzfc is of paramount importance for the understanding of copper’s catalytic properties and for the rational design of electrocatalysts.

CO is a key intermediate in the electro-oxidation of energy carrying fuels and known to act as a catalyst poison. Single-crystal Cu(111) model catalysts can efficiently electro-oxidize CO in alkaline media,2 where strong surface structural changes are observed under reaction conditions with electrochemical scanning tunneling microscopy (EC-STM). Supported by first-principles microkinetic modelling, we have shown that the concomitant presence of high-energy undercoordinated Cu structures at the surface is a prerequisite for the high activity.

In water electrolyzers, it is possible to produce H2 in the course of the hydrogen evolution reaction (HER), which was studied with Ni(OH)2 and Co(OH)2 modified Cu(111) electrodes in alkaline media.
3 Strong morphological changes upon adatom modification lead to a significant HER rate enhancement. Intriguingly, this is induced through a decrease of the electric field strength negative of the pzfc. This implies an easier reorganization of the interfacial water molecules facilitating charge transfer through the double layer, and thus enhancing the efficiency of electrocatalytic reactions. The tendency of Cu(111) to restructure is found to dominate its electrochemical properties. The structural changes of the electrode surface are intimately related to the electric field at the solid/liquid interface and to its electrocatalytic activity, in general.

References:

[1] A. Auer, X. Ding, A. S. Bandarenka, J. Kunze-Liebhäuser, J. Phys. Chem. C 125 (2021) 5020.

[2] A. Auer, M. Andersen, E.M. Wernig, N.G. Hörmann, N. Buller, K. Reuter, J. Kunze-Liebhäuser, Nature Catal. 3 (2020) 797.

[3] A. Auer, F.J. Sarabia, D. Winkler, C. Griesser, V. Climent, J.M. Feliu, J. Kunze-Liebhäuser, ACS Catal. 11 (2021) 10324.

Figure 1
(Invited) Lithium Metal Nucleation and Growth on Conductive Substrates— a Multi-Scale Understanding from Micro, Meso, to Macro-Scales
Authors: Liaw Boryann (Bor Yann)
Published: July 2022

Repetitive lithium (Li) metal deposition and stripping on conductive substrates such as copper is a critical process involved in the rechargeable Li batteries for high energy applications. Most of the time, the reversibility of this deposition and stripping process by electrochemical methods is of paramount importance for long life performance of these batteries. Solid electrolyte interphase (SEI) formation and the dendritic formation of Li whiskers are often cited as the challenges in achieving a uniform, reversible Li deposition and stripping in the process, rendering a short life duration of these batteries for practical applications. The fundamental question of how Li metal nucleates and grows on the conductive substrate has not been well understood until some recent experiments and in situ, operando observations [1,2] began to shed light on this process to offer some clues how to control the morphology of the Li deposition and stripping process.

Here, a collection of experimental evidence and molecular dynamics simulations are presented to provide some insight of this seemingly straightforward process of elemental metal deposition. An explanation to peel off the mystery of the Li nucleation and growth from the atomic level to the micro (<20 nm), meso (20-100 nm), and the macro-scale (>100 nm) is offered to provide some guidance of the control needed to regulate the morphology. Success to demonstrate some highly dense and reversible Li deposition and stripping is shown.

References:

Fang, B. Lu, G. Pawar, M. Zhang, D. Cheng, S. Chen, M. Ceja, J.-M. Doux, M. Cai, B. Liaw, Y. S. Meng, “Pressure-tailored highly-reversible lithium metal electrode for rechargeable lithium batteries.” Nat. Energy 6 (2021) 987–994. https://doi.org/10.1038/s41560-021-00917-3

Wang, G. Pawar, Y. Li, X. Ren, M. Zhang, B. Lu, A. Banerjee, P. Liu, E. J. Dufek, J-G. Zhang, J. Xiao, J. Liu, Y. S. Meng, B. Liaw, “Glassy Li metal anode for high-performance rechargeable Li batteries.” Nat. Mater. 19 (2020) 1339–1345. https://doi.org/10.1038/s41563-020-0729-1
Adsorption-Mediated Electrochemical Atomic Layer Deposition of Gold
Authors: Wasalathanthri Dona Ruwani N. , Gong Yukun , Biener Monika M. , Ivanovskaya Anna N. , Dudukovic Nikola A. , Akolkar Rohan
Published: July 2022

Electrochemical atomic layer deposition (e-ALD) is an effective method for achieving atomic monolayer-by-monolayer deposition of metals. In this presentation, we will discuss the mechanistic events underlying gold (Au) e-ALD. The e-ALD process involves lead underpotential deposition (PbUPD) followed by spontaneous redox replacement (SLRR) of PbUPD by Au. During Au e-ALD, a unique three-stage mass transient is observed. Using voltammetry, electrochemical quartz crystal microgravimetry (e-QCM), and chronoamperometry, we present an in-depth study of the characteristics of this mass transient during Au e-ALD. Adsorption of Au+3-ligand complex(es) (Au-L) on the Au surface is shown to play a key role in the Au-ALD process. The adsorbed Au-L species are reduced in stage I while a PbUPD adlayer is formed. The SLRR of PbUPD adlayer by nobler Au occurs in stage II, followed by the re-adsorption of the Au-L species in stage III. A quantitative analysis of the deposit mass under different conditions allows estimation of the average molecular weight of the adsorbed Au-L complexes. Ramifications of such adsorption-mediated deposition to thickness uniformity, conformality and film roughness will be discussed.

Figure 1
Lifting Polyether Suppression during Cu Electrodeposition
Authors: Moffat Thomas P , Braun Trevor Michael , Raciti David , Liu Guo Kun , Ou Yang Liang Yueh , Osborn William , Richter Lee J. , Hight Walker Angela , Josell Daniel
Published: July 2022

The manufacturing of semiconductor devices involves electrodeposition of copper interconnects from additive containing electrolytes. The process depends on additives that affect the local deposition rate to yield void-free superconformal or bottom–up filling of trenches and vias. Useful quantitative surfactant conservation models are available for describing the filling of high aspect ratio features ranging from nanometers (on-chip wiring) to micrometers (through-silicon-vias) to millimeters (printed circuit boards). This includes the curvature enhanced adsorbate coverage (CEAC) model as well as the additive derived S-shaped negative differential resistance (S-NDR) description of film growth and feature filling. Nonetheless, much remains to be known about the operational limits of these constructs as well as the molecular nature of the competitive, co-adsorption dynamics of the additives and their impact on metal deposition. This lecture will detail recent experiments that reveal the important role of competitive, co-adsorption of polyether, Cl-, SPS and LEV additives in controlling the hydrophilicity of the interface and thereby the rate of metal deposition and its morphological and microstructural evolution.
Enhanced Safety, High-Rate and High-Voltage Performance of a Lithium-Ion Battery Using Nonflammable Liquid Electrolyte
Authors: An Kihun , Tran Yen Hai Thi , Kwak Sehyun , Park Seong Jun , Song Seung-Wan
Published: July 2022

These days lithium-ion battery (LIB) market is rapidly expanding by electric mobilities and stationary energy storage system industries. One of the biggest challenges in the research and development of advanced LIB is to achieve simultaneously outstanding energy density, cycle life, charge rate, and safety. For fast charging, battery chemistry and reaction kinetics are being evolved from the current hours scale toward minutes scale charging. In the LIB electrolyte perspective, the conventional carbonate-based liquid electrolyte has several limitations in safety and high-rate and high-voltage performance, due to low thermal and anodic stabilities under extreme operation conditions like high temperature, high-current, and high-voltage. To mitigate those issues, we have been developing new and safe electrolyte without any trade-off with cycling performance and energy density of Li-ion batteries. Herein, we present high-rate and high-voltage cycling performance and high safety of nickel-rich cathode-based lithium-ion full-cell fabricated with nonflammable liquid electrolyte. The correlation between the stability of nonflammable liquid electrolyte and its derived solid electrolyte interphase (SEI) and performance will be discussed in this meeting.

Acknowledgements

This research was supported by the National Research Foundation grant funded by the Ministry of Science and ICT (No. 2019R1A2C1084024).
Hybrid Halide Solid Electrolytes and Bottom-up Cell Assembly Enable High Voltage Solid-State Lithium Batteries
Authors: Zahiri Beniamin , Kiggins Chadd , Damien Dijo , Caple Michael , Patra Arghya , Juarez Yescaz Carlos , Cook John B. , Braun Paul V.
Published: July 2022

Interface between halide based solid electrolytes and layered transition metal oxide cathodes has been found to be electro-chemically stable due to stability of chloride compounds, in particular, at >4V range. The extent of interfacial stability is correlated with the type of cationic and anionic species in the solid electrolyte compound, a fact supported by theoretical prediction and yet, not accurately measured in composite cathode mixtures. By altering the architecture of cathode into a dense additive-free structure, we have identified differences in interfacial stability of chloride compounds which are hidden in composite cathode formats. In this work, we report the use of dense cathode to track the electrochemical evolution of interface between a hybrid halide solid electrolyte composed of chloride and fluoride species. Introducing fluoride compounds is known to be a promising method to expand the oxidation stability while the nature of such expansion is found to be related to kinetics rather than thermodynamics, we report. Furthermore, fluorination of solid electrolyte is generally accompanied with loss of ionic conductivity due to strong electronegative fluoride ions. We demonstrate a fundamental change of solid-state battery assembly from conventional electrolyte pelletizing followed by electrode placement, to a bottom-up assembly route starting with dense cathode, thin (<20µm) layer of SE and anode addition, which compensates for the suppressed conductivity of fluorinated halide solid electrolytes. Through extensive characterization, compositional optimization, and electrochemical interfacial analysis, we demonstrate stable cycling of LiCoO2/hybrid halide solid electrolyte up to 4.4V vs. Li. Our findings pave the way for expanding the voltage stability of solid electrolytes without compromising the cell performance due to ionic conductivity overpotential issues.
Cyclic Carbonate-Based, Single-Ion Conducting Polymer Electrolytes for Li-Ion Batteries: Battery Performance
Authors: Park Habin , Engler Anthony , Liu Nian , Kohl Paul
Published: July 2022

Solid polymer electrolytes (SPEs) are a pathway for safe, and high energy and power lithium batteries due to their thermal stability and low vapor pressure. Although polymers can be flexible and dimensional stability, it is lithium dendritic suppression can be a challenge for any electrolyte. Conventional SPEs have both mobile cations and anions, which migrate and cause concentration polarization. The low transference number for lithium ions in an electrolyte contributes lithium concentration gradients causing concentration polarization and lithium dendrites [1,2]. Single-ion conducting SPEs have been reported to demonstrate lithium ion only conduction in the electrolyte as well as retain their high mechanical stability during cycling. However, their low ionic conductivity is due to stationary phase of the tethered anion in the polymer matrix and cation-anion complexation [3].

In this study, a cyclic carbonate neutral moiety was included in the SPE to help dissociate the lithium cation from the tethered anion matrix to increase the ionic conductivity and help form the solid electrolyte interphase (SEI) layer. The cyclic carbonate unit in the SPE is similar to the cyclic carbonate solvent in a conventional lithium ion battery and could participate in the solvation of the lithium cation in the SPE. The cyclic carbonate monomer in the SPE can participate in SEI-forming electrochemical reactions on the electrode surface and suppress undesirable side reactions and lithium dendritic growth. Satisfactory level of rate and cycling performance was achieved with the novel neutral monomers in the single-ion conducting SPEs.

[1] H. Zhang, C. Li, M. Piszcz, E. Coya, T. Rojo, L.M. Rodriguez-Martinez, M. Armand, Z. Zhou, Chem. Soc. Rev. 2017, 46, 797-815.

[2] F. Ahmed, I. Choi, M.M. Rahman, H. Jang, T. Ryu, S. Yoon, L. Jin, Y. Jin, W. Kim, ACS Appl. Mater. Interfaces
2019, 11, 34930-34938.

[3] D.-M. Shin, J.E. Bachman, M.K. Taylor, J. Kamcev, J.G. Park, M.E. Ziebel, E. Velasquez, N.N. Jarenwattananon, G.K. Sethi, Y. Cui, J.R. Long, Adv. Mater.
2020, 32, 1905771.
(Invited, Digital Presentation) Pushing the Limits of High Nickel NMC Cathodes
Authors: Whittingham Stan , PEI BEN , Buyuker Isik , Lee Krystal , Xin Fengxia , Zhou Hui
Published: July 2022

Lithium-ion batteries now dominate electrochemical energy storage for vehicle propulsion and grid storage in addition to portable electronics. In 2022, they celebrate their 50th anniversary, and yet still achieve only 25% of their theoretical energy density. The dominant anode and cathode today are graphitic carbon and the layered NMC oxides, LI[NiMnCoAl]O2. Both need improving. Most of the carbon in the anode must go, and the NMCs need pushing to their limit and at the same time eliminating cobalt. I will today discuss the challenges faced as we push the limits of the NMCs to their limits, > 80% lithium cycling, and Ni>0.8 and Co <<0.1. The higher the Ni content the lower the charging voltage needed for a given cycling capacity, but the greater its surface and bulk reactivity. The issues discussed will include 1stcycle loss [1], high rate capability [2], cathode stability [3], and surface/bulk reactivity and the impact of surface/bulk modification [4,5] and the micron-size single crystals vs meatballs on these [6]. This work is being supported by DOE-EERE-BMR-Battery500 consortium.

[1]. Hui Zhou, Fengxia Xin, Ben Pei, M. Stanley Whittingham, “What Limits the Capacity of Layered Oxide Cathodes in Lithium Batteries?”, ACS Energy Lett. 2019, 4: 1902−1906.

[2]. Chunmei Ban, Zheng Li, Zhuangchun Wu, Melanie J. Kirkham, Le Chen, Yoon Seok Jung, E. Andrew Payzant, Yanfa Yan, M. Stanley Whittingham, and Anne C. Dillon “Extremely Durable High-Rate Capability of a LiNi0.4Mn0.4Co0.2O2 Cathode Enabled by Single–Wall Carbon Nanotubes”, Advanced Energy Materials, 2011, 1: 58-62.

[3]. Hyung-Joo Noh, Sungjune Youn, Chong Seung Yoon, Yang-Kook Sun “Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = ¼ 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries”, J. Power Sources, 2013, 233: 121-130.

[4]. Fengxia Xin, Hui Zhou, Yanxu Zong, Mateusz Zuba, Yan Chen, Natasha A. Chernova, Jianming Bai, Ben Pei, Anshika Goel, Jatinkumar Rana, Feng Wang, Ke An, Louis F. J. Piper, Guangwen Zhou, and M. Stanley Whittingham, “What is the Role of Nb in Nickel-Rich Layered Oxide Cathodes for Lithium-Ion Batteries?”, ACS Energy Letters, 2021, 6: 1377-1382.

[5]. Ben Pei, Hui Zhou, Anshika Goel, Mateusz Zuba, Hao Liu, Fengxia Xin, and M. Stanley Whittingham, “Al Substitution for Mn during Co-Precipitation Boosts the Electrochemical Performance of LiNi0.8Mn0.1Co0.1O2”, J. Electrochemical Society, 2021, 68: 050532.

[6]. Yujing Bi, Jinhui Tao, Yuqin Wu, Linze Li, Yaobin Xu, Enyuan Hu, Bingbin Wu, Jiangtao Hu, Chongmin Wang, JiGuang Zhang, Yue Qi and Jie Xiao, “Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode”, Science, 2020, 370: 1313-1317.
(Invited) Advanced Characterizations of Interfaces in Solid-State Batteries
Authors: Yao Yan
Published: July 2022

The complex origins of solid-state battery failure call for multidimensional diagnostics utilizing a combination of tools that can quantify the void and dendrite formation, identify the chemical and mechanical natures of the Li dendrites and electrolyte decomposition products. However, there is lack of tools that connect multiple techniques with desirable length scale, resolution and sensitivity for characterizing solid-state batteries. We will present out effort in developing an air-free vessel with an in-situ cell test platform connecting FIB-SEM tomography, ToF-SIMS, and in-SEM nanoindentation for structural, chemical, and mechanical characterizations of solid-state Li batteries. We fabricated solid-state micro-cells with electrochemical performance on par with their bulk-type counterparts. Electrochemical tests with precise temperature control, external pressure, and pressure monitoring of thin solid-state cells were demonstrated with structural, chemical and mechanical characterizations.

This work was supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Vehicle Technologies Program under Contract DE-EE0008864.
Application of Tetraethylsulfamide (TES) As a Cathode Additive in Cylindrical Cells
Authors: Ma Xiaowei , Wood Bryan D. , Way Brian
Published: July 2022

Recently, sulfonamides have been shown to be promising electrolyte components due to their high chemical and electrochemical stability in lithium batteries [1, 2]. The electrolyte stability becomes critical when applying high voltage and/or utilizing Ni-rich layered oxides in high energy density lithium-ion batteries. Another approach to successful Ni-rich cathode performance is to develop a stable and effective cathode electrolyte interphase (CEI). Given the success of sultones and sulfates in this regard [3, 4], it is hypothesized that nitrogen analogs, like sulfonamides, could be tailored to provide a similar benefit. Indeed, Yim et al. [5, 6] have shown that N,N,N’,N’-tetraethylsulfamide (TES) forms a CEI on NMC811 that imparts high voltage cycling stability and less cathode corrosion. Our earlier studies of TES with Ni-rich NCA also formed a favorable CEI and these results are the topic of this presentation.

Herein, we examine the performance of 0 - 4 wt.% TES in our commercially available, high power INR18650-P28A. These cells contain a composite SiO/graphite anode in addition to a Ni-rich cathode. As shown in Fig 1, TES significantly decreased the impedance of the cathode interface after conditioning compared to the control electrolyte. Thereafter, cells containing up to 2%TES show improved capacity retention during long-term high-rate cycling (+1C/-80W). Part of this success was due to a suppression of resistance growth during cycling by TES. Fast charge cycling (+3C/-2C), however, was moderately impaired with increased TES. Considering the largely reduced impedance of the cathode, fast-charge performance may have suffered due to anode rate limitations. These results will be discussed as well as gas generation, storage performance, and additional rate and cycling tests.

[1] Shuting Feng, Mingjun Huang, Jessica R. Lamb, Wenxu Zhang, Ryoichi Tatara, Yirui Zhang, Yun Guang Zhu, Collin F. Perkinson, Jeremiah A. Johnson, Yang Shao-Horn. Chem, 5, 2630-2641 (2019)

[2] Weijiang Xue, Mingjun Huang, Yutao Li, Yun Guang Zhu, Rui Gao, Xianghui Xiao, Wenxu Zhang, Sipei Li, Guiyin Xu, Yang Yu, Peng Li, Jeffrey Lopez, Daiwei Yu, Yanhao Dong, Weiwei Fan, Zhe Shi, Rui Xiong, Cheng-Jun Sun, Inhui Hwang, Wah-Keat Lee, Yang Shao-Horn, Jeremiah A. Johnson, Ju Li. Nature Energy, 6, 495-505 (2021)

[3] Koji Abe, Manuel Colera, Kei Shimamoto, Masahide Kondo, Kazuhiro Miyoshi. Journal of Electrochemical Society, 161 (6) A863-A870 (2014)

[4] Jian Xia, N. N. Sinha, L. P. Chen, J. R. Dahn. Journal of Electrochemical Society, 161 (3) A264-A274 (2014)

[5] Kwangeun Jung, Taeeun Yim. Journal of Alloys and Compounds, 834,155155 (2020)

[6] Ji Won Kim, Kwangeun Jung, Taeeun Yim. Journal of Mater. Sci & Tech. 86, 70-76 (2021)

Figure 1
Design Framework for Cobalt and Ni-Free High-Capacity Lithium-Ion Cathodes
Authors: Nanda Jagjit
Published: July 2022

Growing demand for Lithium-ion batteries for electric transportation and grid-scale storage will inevitably put resource constraints in terms of availability of key critical battery materials such as cobalt, nickel, lithium, and graphite. Specifically limited global reserve of elements such as cobalt and nickel will lead to severe supply chain issues driving the cost and contributing to market uncertainty. Given such scenario, there has been a significant effort in the global research community to develop high performance battery materials derived from relatively earth abundant elements. The talk will highlight ongoing research at PI’s Laboratory and collaborators on developing cobalt-free disorder rock salt (DRX) cathodes for next generation Li-ion. Most practical Li-ion cathode materials have well-ordered structures (e.g., spinel, layered, olivine), while the DRX compounds do not require any cation ordering. Instead, Li transport is achieved by percolation through a cation-disordered within the dense crystalline rock salt structure. Since DRX compounds do not necessitate a layered structure, they do not necessarily require cobalt metal and can be synthesized from an extremely wide variety of common metals, including Ti, Mn, Ni, Al, Nb, Mo, V, Zr, etc. Therefore, such class of materials provides plenty of chemical options for cathode design for Li-ion. Another key enabling aspect for this class of cathodes is the role of fluorine in stabilizing the high voltage oxygen redox and capacity retention. The talk will focus specifically on synthesis and structural design of Li-Mn-Ti-OF based DRX compositions and pathways for improving high voltage redox and stability.

This work performed at Oak Ridge National Laboratory is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program, of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725
(Digital Presentation) Surface Modifications of Cathodes By Coating: A Step Towards Improving the Electrochemical Performance of Lithium Ion Batteries (LIBs)
Authors: Kaur Gurbinder , Duncan Kelsey , Gates Byron D.
Published: July 2022

Lithium-ion batteries (LIBs) have been widely utilized as power sources for mobile devices. Recently, their use has been expanded to large-scale applications such as electric vehicles (EVs) and energy storage systems (ESSs). These batteries have dominated the energy industry due to their unmatchable properties that include a high energy density, a compact design, and an ability to meet a number of required performance characteristics in comparison to other rechargeable systems. Two vital parameters for LIBs are their stable and safe operation. Since, the cathode serves as a central component of LIBs, the overall cell performance is significantly affected by the chemical and physical properties of the cathode. Cathodes tend to react with the electrolytes and, hence, undergo surface modifications accompanied by degradation. These side-reactions result in an erosion of battery performance and rate capability, thereby causing a reduced battery life and power capacity. Surface coating is the most simple, economical and effective method to protect the cathode surface from degradation and detrimental interfacial reactions with the electrolyte. For the present investigation, a variety of coatings have been used to coat cathode surface. The aim is to explore the effect of these coatings on the physicochemical characteristics as well as electrochemical and thermal properties of spinel cathode using characterization techniques like scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD) and differential thermal analysis (DTA)/ thermogravimetric analysis (TGA).
(Digital Presentation) Temperature Rise during High-Power Pulses of Lithium-Ion Batteries
Authors: Knehr Kevin , Kubal Joseph , Dees Dennis , Nelson Paul , Ahmed Shabbir
Published: July 2022

Lithium-ion batteries currently dominate the light-duty electric vehicle (EV) market due to their high energy density, low self-discharge, and high efficiency. Because of these advantages, Li-ion batteries are now being explored for next-generation EV applications like heavy trucks and aerial vehicles. The new applications present design challenges somewhat different from light-duty, road vehicles. For instance, aerial EVs during take-off and landing or heavy trucks on lengthy inclines/declines require high power (or regenerative) pulses for >1 minute. These long-duration, high power pulses may lead to significant temperature rise that could damage the battery and/or produce unsafe conditions resulting in thermal runaway. Accurate estimations of the temperature rise during these pulses are important for initial studies focused on assessing the validity of Li-ion batteries in these and other applications.

This work starts by demonstrating how the accuracy of approximating the temperature rise using Joule heating – i.e., I2R, where I is the applied current and R is the electrochemical resistance – decays considerably for high power pulses. A 3-D thermal-electrochemical model of an NMC532-Graphite pouch cell is then used to explain the causes of the deviation. It is shown that a combination of transport in the electrolyte and self-heating cause variations in the resistance during the pulse, which invalidate the Joule heating approximation. Insights from these results are used to develop a correlation for the temperature rise during high power pulses. The correlation provides an improved estimation of the temperature using minimal experimental data for the area specific resistance of the cell.
Investigation and Characterization of in-Situ Polymer Brush SEI Core Shell Layer Effects on Si Anode Material and Its Battery Performance
Authors: Hailu Alem Gebrelibanos Gebrelibanos , Wang Fu-Ming
Published: July 2022

Silicon is a promising material for lithium-ion batteries due to its super high capacity.1 However, the volume expansion and the pulverization of Si limit its perforamce.2 This study investigates the effect of a polymer brush core-shell structure of Si as an anode material. The polymer brush is designed through Si-C covalent bond of vinyl monomers by thermal hydrosilylation reaction. According to the results, the PBCS structure provides three significant functions on Si particles because of the intramolecular effect of hydrogen bonding with PBCS and binder delivers a good dispersion in the slurry, a mechanical protection during cycling, and excellent ionic conductivity for high-rate tests. Compared with the unmodified electrode (SiNP), the modified electrodes (SiNP-M1 and SiNP-M2) incorporating the PBCS provides better initial columbic efficiency of 87.1% with the first discharge capacity of 1988.9 mAh g-1. The TEM and operando TXM results display that the PBCS structure significantly protects the nano Si from cracking owing to the high elastic function and intramolecular hydrogen bonding effect of the PBCS. Operando X-ray diffraction is also used to provide the phase information of the Si electrodes. With this novel PBCS-Si material, a high energy density lithium-ion battery contains pure Si can be expected.

Reference

Li, C.; Shi, T.; Li, D.; Yoshitake, H.; Wang, H., Effect of surface modification on electrochemical performance of nano-sized Si as an anode material for Li-ion batteries. RSC Advances
2016,
6 (41), 34715-34723.

Gao, Y.; Yi, R.; Li, Y. C.; Song, J.; Chen, S.; Huang, Q.; Mallouk, T. E.; Wang, D., General Method of Manipulating Formation, Composition, and Morphology of Solid-Electrolyte Interphases for Stable Li-Alloy Anodes. J Am Chem Soc
2017,
139 (48), 17359-17367.

Figure 1