bluuebunny/crossref_metadata_2025_split huggingface dataset:
Adapting Simultaneous in Operando Electrochemical Quartz Crystal Microbalance (EQCM) and Electrochemical Impedance Spectroscopy (EIS) to Studies of SEI Layer Formation on Amorphous Silicon Anodes
Authors: Morris Louis Vincent , Ortiz-Ledon Cesar , Hamers Robert J 
Published: July 2022

Lithium-ion Batteries (LIBs) are the electrochemical energy storage technology of choice for an incredible range of technologies, from handheld consumer electronics to electric vehicles. Since their introduction, the application of these batteries has been limited by their energy density, which is in turn currently gated by the low theoretical energy density of the graphite anodes that are standard in the field. Si has long been targeted as a next generation anode material, with a theoretical energy density almost 10 times larger than graphite, however uncontrolled electrolyte decomposition on its surface has caused poor cycle life and low columbic efficiencies in Si-containing cells1. In this work, a new class of organosilicon (OS) additives were introduced to the Si anode literature and their effect on the first-cycle electrochemistry on model anode surface was explored using in operando electrochemical quartz crystal microbalancing (EQCM) and electrochemical impedance spectroscopy (EIS). Ex situ x-ray photoemission spectroscopy (XPS) was also used to investigate the differences in chemical composition of solid electrolyte interface (SEI) layers formed in the presence and absence of additive. EQCM-EIS experiments demonstrated an increase in cell impedance early in the cycle, which lead to the suppression of early electrolyte decomposition on the model anode surface. Subsequently, lithiation and delithiation proceeded more efficiently and with lower impedance in additive-treated cells. Finally, XPS investigations of the SEI composition revealed that OS-treated cells create thinner SEI layers that were richer in LiF and contained less organic material than cells without OS.
(1) Jin, Y.; Zhu, B.; Lu, Z.; Liu, N.; Zhu, J. Challenges and Recent Progress in the Development of Si Anodes for Lithium-Ion Battery. Adv. Energy Mater.
2017, 1700715, 1–17. https://doi.org/10.1002/aenm.201700715.
Changes in Heat Generation during Degradation of Commercial Lithium-Ion Batteries
Authors: Spitthoff Lena , Wahl Markus Solberg , Vie Preben J. S. , Burheim Odne Stokke 
Published: July 2022

The performance, lifetime and safety issues of lithium ion batteries (LIB) are strongly linked to temperature and many studies in the past three decades have been devoted to improving the understanding of thermal behaviour of LIB at cell and pack level1. We present ageing and diagnostic data of a commercial pouch LIB and present a thermal battery model. The thermal battery model is used to discuss changes in different heat generation sources alongside battery ageing measurements. It further allows for a differentiation between temperature induced and C-rate accelerated ageing.
A selection of LCO-graphite cells was aged and cycled in the full state-of-charge window at 5, 15, 25, 35 and 45°C. We compare constant current cycling with charge and discharge rates of 1 C, 2 C and 3 C, and constant power discharging. The cells were monitored in detail during the ageing including surface. The performance at lower C-rates, internal resistances and the changes in cell thickness were obtained as functions of changes in state-of-health. Thermal conductivity measurements were performed for the electrode material at end and beginning of life.
A 1D analytical thermal model is used for a discussion about the impact of the heat sources, the effect of a change in heat transport with ageing due to decreased thermal conductivities, and the impact of internal temperature gradients on ageing.
By utilizing the thermal battery model, it is possible to analyze the effect of the different heat sources on the overall battery temperature as well as degradation dependent changes in heat generation. The heat sources included in the model are the ohmic heat produced, heat production due to overpotential, and reversible entropic heat due to the electrode reactions, where the entropic heat can both act as a heat source and heat sink. The transfer of heat inside the battery is described using Fourier’s second law.
These heat and temperature effects allow further to differentiate between temperature induced and C-rate accelerated ageing. Together with evaluating the impact of temperature gradients over the cell compared to the maximum cell temperature, this allows to estimate the impact of an improved thermal management system.

References

1 Spitthoff, L.; Burheim, O.S.; Shearing, P.R. Temperature, Ageing and Thermal Management of Lithium-Ion Batteries. Energies 2021, 14, 1248. https://doi.org/10.3390/en14051248
Investigating Li Plating Distribution Caused By a Thermal Gradient through Modelling, Differential Voltage, and Post-Mortem Analysis
Authors: Tomaszewska Anna , Doel Robert , Parkes Michael , Offer Gregory James , Wu Billy 
Published: July 2022

Relatively slow charging speeds are often quoted as a key barrier to customer acceptance of EVs. Currently, the charging rates are limited primarily by the risk of lithium plating. While traditionally lithium plating has been associated with low temperature charging, recent reports point to the fact that thermal heterogeneity can significantly affect the plating behaviour, sometimes making it more likely or accelerated in the warmer regions in a cell [1][2]. In EVs, through-plane thermal gradients often develop across individual pouch cells due to the widespread use of surface cooling, particularly during fast charging, when the heat generation rates are also increased. This work investigates the effects of such through-plane thermal gradients on the lithium plating behaviour using a multilayer 2D electrochemical-thermal model and high-rate cycling experiments. The results show that the thermal gradient can result in preferential plating in either the colder or warmer cell regions, depending on the average cell temperature and the activation energies of solid diffusion and lithium plating. While the diffusion rates are slower in the colder cell layers, warmer ones attract higher currents and either of these effects may dominate the plating behaviour. The experimental validation consists of differential voltage analysis, post-mortem visual examination and measurement of remaining capacity in coin cells harvested from Li-ion cells fast charged under uniform temperatures and under thermal gradients. The limitations of DVA as a technique to quantify lithium plating are highlighted. These stem from the fact that the quantification technique requires assuming that only lithium stripping and no de-intercalation takes place up to the differential voltage minimum. In reality, the current is divided between both reactions, and both the temperature and concentration of the metallic lithium may affect the rate of stripping, shifting the location of the minimum independently of the amount of lithium plated. The results shed light on the effects of thermal gradients on lithium plating behaviour in pouch cells and the challenges associated with quantifying plating with DVA.
References:
[1] – H. Wang, et al., “Underpotential lithium plating on graphite anodes caused by temperature heterogeneity”, PNAS 117, 29453-29461 (2020)
[2] – J. Sieg, et al., “Local degradation and differential voltage analysis of aged lithium-ion pouch cells”, J. Energy Storage 30, 101582 (2020)
(Henry B. Linford Award for Distinguished Teaching) The Role of Electrochemistry in Battery R&D
Authors: Winter Martin , Kasnatscheew Johannes , Heinemann Kerstin , Bartling Vanessa , Ellermann Leonie , Stolz Lukas 
Published: July 2022

Encouragement and motivation of young talents and students to engage in the mesmerizing field of electrochemistry and in particular in electrochemical energy storage is of outmost prominence to generate sustainability in the battery community that is inevitable to guarantee manpower continuity in one of the biggest global challenges of mankind, i.e. climate change and depletion of fossil fuels. Lithium-based batteries are regarded as key energy storage technology for further breakthroughs in energy transition and mobility transition and related R&D.[1] Limitations in typical electrochemical performance criteria, e.g. energy/power density, fast charge capability and cycle life will likely require even more intense R&D efforts in the future.[2] Electrochemistry is not only the basic principle of battery cell operation, but a reliable and frequently underestimated in situ instrument for monitoring and diagnostics.[3, 4]

Alongside with its strong methodological capability, the fundamental principles of electrochemistry for the understanding of practical battery cells will be emphasized in this presentation. Fundamental electrochemical relations like Sand`s law, the Nernst equation, Ohm’s law and the rules of Faraday; and in reverse manner, their mindful use in electrochemical methodology can precisely indicate and forecast processes during battery cell application and thus realize a simple and systematic, but at the same time a very effective and impactful R&D approach.[5,6] Consequently, elucidating the role of electrochemistry in energy storage will build a bridge between (simple) electrochemical fundamentals and the rather complex practical behavior of state-of-the-art and future battery systems, thus serving as topical attraction for young talents to enter into one of the most relevant and fascinating fields of natural sciences and engineering.

Reference
s
:

[1] M. Winter, R. J. Brodd Chemical Reviews. 2004, 104, 4245-4269.
[2] R. Schmuch, R. Wagner, G. Hörpel, T. Placke, M. Winter Nature Energy. 2018, 3, 267-278.
[3] R. Nölle, K. Beltrop, F. Holtstiege, J. Kasnatscheew, T. Placke, M. Winter Materials Today. 2020, 32, 131-146.
[4] J. Kasnatscheew, M. Evertz, R. Kloepsch, B. Streipert, R. Wagner, I. Cekic Laskovic, M. Winter Energy Technology. 2017, 5, 1670-1679.
[5] L. Stolz, G. Homann, M. Winter, J. Kasnatscheew Materials Today. 2021, 44, 9-14
[6] F..Holtstiege, A. Wilken A, M. Winter M, T. Placke, Phys. Chem. Chem. Phys.,
2017
, 19, 25905-25918
(Invited) Initial Capacity Loss Mechanism of All-Solid-State Lithium Sulfide Battery Unraveled By in Situ Neutron Tomography
Authors: Yang Guang , Zhang Yuxuan , Self Ethan , Brahmbhatt Teerth , Bilheux Jean-Christophe , Bilheux Hassina , Nanda Jagjit 
Published: July 2022

All-solid-state lithium metal batteries promise a specific energy >500 Wh/kg. A solid-state electrolyte (SSE) plays an irreplaceable role in reaching such an energy density goal. Among different SSE types, the sulfide and thiophosphate-based SSE has emerged as a prominent class of soft ionic conductors. Compared to their ceramic and oxide SSE counterparts, sulfide SSEs provide several favorable advantages, including a) high room temperature ionic conductivity up to 10 mS/cm that is comparable to liquid-based electrolytes; b) ductile and mechanically soft SSE that enables better processible and intimate contact with electrodes; and c) scalability with solution-based low-temperature synthesis route.
However, when paring with a high voltage cathode, such as lithium nickel manganese cobalt oxide (NMC), the (electro)chemical instability of the sulfide SSE at the electrode/SSE interfaces becomes a major challenge to tackle with. The interfacial instability can result in up to 50% initial capacity loss in a Li/sulfide SSE/NMC battery, thereby keeping the sulfide SSEs from commercialization. Herein, by using neutron computed tomography, we trace in situ lithium displacement in an all-solid-state battery composed of a 7Li anode, natLi3PS4(LPS) electrolyte, and a natLiNi0.8Mn0.1Co0.1O2 (NMC811) cathode. We show that after the first galvanostatic charge/discharge cycle, lithium accumulates at the LPS/NMC811 interface and preferably fills in the pre-formed cracks in the cold-pressed LPS SSE pellet. Such irreversible lithium displacement contributes to the initial capacity loss of the Li/LPS/NMC battery. Our findings suggest that to achieve high-capacity retention of an all-solid-state sulfide-based battery using an NMC cathode, the cathode/sulfide interface should be better engineered and the defects of the LPS pellet should be suppressed.
Acknowledgment
This research was conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) and is supported by Asst. Secretary, Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program. This research used resources at High Flux Isotope Reactor, a DOE Office of Science User Facilities operated by the Oak Ridge National Laboratory.
Reinforcing the Li|Li1.3Al0.3Ti1.7(PO4)3 Interfacial Stability By an Ultrathin Multifunctional Polysiloxane-Based Single-Ion Conducting Polymer
Authors: Chen Zhen , Liang Hai-Peng , Stepien Dominik , Lyu Ziyuan , Zarrabeitia Maider , Kuenzel Matthias , Wu Fanglin , Kim Guk-Tae , Passerini Stefano , Bresser Dominic 
Published: July 2022

Lithium metal is considered as one of the most promising anode candidates for high-energy batteries [1-3]. However, safety concerns induced by the formation of Li dendrites largely hinder the practical application of lithium-metal batteries [4]. It is anticipated that the use of non-flammable inorganic solid-state electrolytes can resolve these safety issues [5], but solid ceramic electrolytes generally suffer from poor physical contact with the electrode and poor electro-/chemical stability at the electrolyte|electrode interface [6].
Herein, we report on a thin and flexible hybrid electrolyte composed of NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP), a polymer binder, and a small amount of an ionic liquid-based electrolyte. To reinforce the interfacial stability between LATP and Li, we coat an ultrathin polysiloxane-based single-ion conducting polymer (PSiO) on the Li metal surface via a simple dip-coating method. The implementation of PSiO-coated Li (PSiO@Li) in symmetric PSiO@Li||PSiO@Li cells enables a substantial extension of the cycle life, yielding >2,000 h of stable lithium stripping-plating. The full-cells comprising PSiO@Li as the negative electrode, LiNi0.88Co0.09Mn0.03O2 (NCM88) as the positive electrode active material, and the aforementioned hybrid electrolyte exhibit substantially enhanced rate capability at high dis-/charge rates above 0.5C and greatly prolonged cycle life at 1C. The superior performance achieved herein is mainly attributed to: (1) the prevented direct contact between LATP and Li, thus avoiding the reduction of LATP and the formation of mixed ion-electron conducting interphases; (2) the regulated Li+ flux at the electrode|electrolyte interface, ensuring homogeneous Li+ stripping-plating; and (3) the promoted intimate contact between PSiO and Li via the formation of Si−O−Li bonds.

References

[1] T. Li, X.-Q. Zhang, P. Shi, Q. Zhang, Joule, 3 (2019) 2647-2661.
[2] B. Horstmann, J. Shi, R. Amine, M. Werres, X. He, H. Jia, F. Hausen, I. Cekic-Laskovic, S. Wiemers-Meyer, J. Lopez, D. Galvez-Aranda, F. Baakes, D. Bresser, C.-C. Su, Y. Xu, W. Xu, P. Jakes, R.-A. Eichel, E. Figgemeier, U. Krewer, J.M. Seminario, P.B. Balbuena, C. Wang, S. Passerini, Y. Shao-Horn, M. Winter, K. Amine, R. Kostecki, A. Latz, Energy Environ. Sci., 14 (2021) 5289-5314.
[3] S. Wang, P. Xiong, J. Zhang, G. Wang, Energy Storage Materials, 29 (2020) 310-331.
[4] Z. Yu, Y. Cui, Z. Bao, Cell Rep. Phy. Sci., 1 (2020) 100119.
[5] S. Xin, Y. You, S. Wang, H.-C. Gao, Y.-X. Yin, Y.-G. Guo, ACS Energy Lett., 2 (2017) 1385-1394.
[6] A. Banerjee, X. Wang, C. Fang, E.A. Wu, Y.S. Meng, Chem. Rev., 120 (2020) 6878-6933.
Pursuing of Equi-Atomic Electrodeposited Cu-Co-Fe-Ni Film
Authors: Sun Yunkai , Zangari Giovanni 
Published: July 2022

Composition control of multicomponent electrodeposited alloy films is very challenging. For example, non-linearity between the deposit composition and bath constitution could occur in alloy electrodeposition systems containing Fe and Ni, due to the anomalous codeposition phenomena (which usually means electrodeposition kinetics is controlled by the reduction of intermediates at the surface of cathode rather than the mass-transfer in the diffusion layer). On the other hand, it is still uncertain if the composition of alloy electrodeposition system is chaotic within the experimental errors in the electrolyte preparation and electrodeposition cell setup.
In this presentation, we will introduce some recent explorations in the composition control of the quaternary alloy Cu-Co-Fe-Ni. The initial stage composition will be investigated with cross-section SEM-EDS line-scans, whereas the nonlinearity will be explored with electrodeposition at a fixed duration but different applied potentials, concentrations of depositing species, and supporting electrolytes with different pH buffer capability.
(Digital Presentation) Znni Electroplating from an Ethylene Glycol Based Non-Aqueous Electrolyte for Corrosion Protection
Authors: Bernasconi Roberto , Firtin Fatma Godze , Kahyaoglu Buse , Nobili Luca , Magagnin Luca 
Published: July 2022

ZnNi alloys containing Ni in the 15 - 25 % wt. range have recently attracted the attention of researchers due to their interesting corrosion properties [1]. These materials, when deposited in the form of thin films, find application in a large number of industrial fields: oil and gas, automotive and constructions. ZnNi is normally electrodeposited from aqueous solutions, specifically alkaline cyanide-free or acidic chloride baths. In these electrolytes, plating takes place following a typical anomalous mechanism where the less noble metal (zinc) deposits preferentially [2].
Even though ZnNi plating from water based solution is already implemented at the industrial scale, alternative deposition approaches have been developed in the last few years to further improve ZnNi plating performances. In particular, the use of non-aqueous electrolytes has been investigated by virtue of their significant advantages over water based solutions: wider electrochemical windows, reduced side reactions and low vapor pressure. ZnNi electrodeposition has been attempted from a great variety of such novel baths, mainly including II and III generation ionic liquids [3, 4].
The present work investigates the use of non-aqueous ethylene glycol based electrolytes for the deposition of ZnNi alloys containing Ni in the 15 - 25 % wt. range. The use of ethylene glycol as solvent introduces many advantages with respect to aqueous solutions: low oxygen contamination, high deposits purity and no pH dependance [5]. ZnNi codeposition from ethylene glycol baths containing ZnCl2 and NiCl2 was studied employing cyclic voltammetry and thin layers were deposited under potentiostatic control. Deposition potential was varied and its influence on final composition and morphology was determined. Compositional data evidenced the occurrence of a potential dependent anomalous codeposition mechanism analogous to the one reported in water based electrolytes. Addition of an additive (NH4Cl) to enhance surface morphology was attempted as well [4]. Phase composition was investigated using XRD and the results obtained demonstrated the presence of a metastable γ-ZnNi phase, which has already been observed in the case of ZnNi plated from alkaline aqueous solutions [6]. Finally, corrosion behavior of the ZnNi layers obtained from ethylene glycol was assessed and compared with equivalent coatings deposited from commercial ZnNi aqueous solutions.
[1] M. Gavrila et al., Surf. Coat. Technol. 123 (2-3), 164-172 (2000)
[2] G. Roventi et al., J. Appl. Electrochem. 30 (2), 173-179 (2000)
[3] K. K. Maniam et al., Appl. Sci. 10, 5321 (2020)
[4] S. Fashu et al., Trans. Nonferrous Met. Soc. China 25 (6), 2054-2064 (2015)
[5] G. Panzeri et al., Electrochim. Acta 271 (1), 576-581 (2018)
[6] S. Ieffa et al., Trans. Inst. Met. Finish. 94, 321-324 (2014)
Understanding Key Limiting Factors of Electrode and Cell Designs in Solid-State Lithium Batteries
Authors: Yim Chae-Ho , Abu-Lebdeh Yaser 
Published: July 2022

Solid-state batteries (SSBs) use solid electrolytes (SE) to replace flammable liquid electrolytes that result in safer batteries with increased energy density enabled by lithium metal as an anode. Even though there have been recent major breakthroughs at the material level and some at the cell level, there are still many more challenges to overcome that are mostly related to the solid-solid interfaces besides the grand challenge of manufacturing these type of batteries with or without existing manufacturing processes with the promised energy density ( > 400Wh/Kg) at targeted low costs (< 100$/KWh). For this to happen, it is important to look into all the changes that need to be made at the material, electrode and cell levels compared to what is currently used in Li-ion cells and critically evaluate their impact on the cell energy density. In this work, we have first used an equation that we have previously modified and used to calculate the impact of Si content in Si-graphite composite on the full-cell energy density (2) to evaluate the impact of the following parameters (type of anode-or no anode- and cathode materials. N/P ratio, thickness of SE and most importantly the composite cathode formulation on the full-cell energy density. In the latter, we have evaluated the thickness of two electrodes, amount and volume of cathode active material, and amount of catholyte). We will present the impact of each of the above-mentioned factors on the cell energy density supported by data from half and full cells using composite cathodes coupled with and without lithium metal as an anode.
References:
(1) Mauro Pasta et al 2020 J. Phys. Energy 2 032008.
(2) Chae-Ho Yim, Svetlana Niketic, Nuha Salem, Olga Naboka and Yaser Abu-Lebdeh, 2017, J. Electrochem. Soc. 164 A6294.