bluuebunny/crossref_metadata_2025_split huggingface dataset:
Operando High-Temperature X-Ray Absorption Spectroscopy of LiNiO2 Cathode Material during Synthesis
Authors: Kubota Kei , Ichihara Fumihiko , Masuda Takuya 
Published: February 2024

The increasing demand for higher energy density in batteries for automotive applications has led to a trend toward increasing the Ni content in layered oxide cathode materials to increase their reversible capacity. However, LiNiO2, which has the highest Ni content, shows a faster capacity drop during charge-discharge cycling, which is attributed to its inherent structural instability in both the pristine and delithiated states. Therefore, to address the former issue and to better understand the appropriate synthesis conditions for LiNiO2, we have studied the changes in the local structure of LiNiO2 during the synthesis process using operando analysis techniques.
Recently, high temperature in situ X-ray diffraction during LiNiO2 synthesis was reported by Bianchini [1] and Weber [2], which confirmed the loss of lithium and oxygen and the migration of Ni to Li layers above 700 °C. To further understand the mechanism of Li/Ni mixing and oxygen loss, operando high-temperature X-ray absorption spectroscopy (XAS) was performed during the synthesis of LiNiO2 to clarify the electrical structure of Ni at high temperatures.
Pre-heated Li
x
NiO2 (x = 0.76, 1.01, 1.26, and 1.51) precursors were prepared by heating LiOH·H2O and Ni(OH)2 at 480 °C for 24 h in air. The precursor was pelletized and set in a quartz sample holder. Operando high-temperature Ni K-edge XAS spectra of the precursor were obtained at BL9A and BL12C in Photon Factory (PF), High Energy Accelerator Research Organization (KEK) by a transmission mode. The operando spectra of all samples except Li/Ni = 0.76 revealed a clear edge shift to the lower energy side corresponding to nickel reduction above 700 °C. The Li/Ni = 0.76 sample has a lithium-deficient composition and Ni is not oxidized to Ni3+ below 700 °C, so the Li/Ni = 0.76 sample has almost no Ni K-edge energy shift above 700 °C. These results suggest that Ni in LiNiO2 is reduced above 700 °C even in an oxygen atmosphere, regardless of whether the Li/Ni ratio is greater than 1. The Ni reduction above 700 °C is probably the cause of the Li/Ni mixture.
Reference
[1] M. Bianchini, J. Janek, et al., Angew. Chem., Int. Ed., 58, 10434 (2019).
[2] R. Weber, J. R. Dahn, et al., J. Electrochem. Soc., 167, 100501 (2020).
Development of Graphite Anodes from Coal Derived Carbon
Authors: Paul Abigail , Magee Regan , Wilczewski Warren , Wolfe Kody D , Wichert Nathan , Wang Fengkun , Trembly Jason , Staser John A. , Garrick Taylor R. 
Published: February 2024

As demand for energy storage expands, securing reliable supply-chains for raw battery materials is critical in mitigating the threats of delayed manufacturing and inflated manufacturing costs. These issues have pushed researchers and industry to consider alternative sources for traditional lithium-ion battery materials, such as graphite. Commonly available sources of graphite for Li-ion anodes include natural graphite and petroleum coke derived synthetic graphite. While many carbon sources have been studied, most require complicated processing and result in sub-par graphite anode materials. This talk highlights raw coal and coal derived materials as promising graphite sources thanks to their abundance of sp2 hybridized carbon, resulting in simpler processing, and low material costs.
We show that coal derived graphite can be implemented as a lithium-ion anode, however, many chemical, microstructural, and morphological considerations are necessary to compare with commercial graphite performance. Key topics of this talk include i) the processing steps necessary for achieving high-performing coal-derived graphite, ii) chemical, microstructural, and morphological graphite characterization, and iii) comparative performance of coal-derived graphites and commercial graphite as lithium-ion anodes. Characterization of the anodes’ performance includes gravimetric capacity, initial capacity loss, coulombic efficiency, internal resistance, intercalation energetics, and pseudo-open circuit potential characterization. Emphasis is placed on the careful consideration and effects of fundamental anode properties (particle size, surface area, etc.) because they are crucial in determining the viability of alternative graphite sources for lithium-ion battery anodes.
Electrochemical Synthesis of Nano-Structured Si and Graphene Composite for Li Ion Battery
Authors: Patel Yashkumar , Vanpariya Anjaliben , Mukhopadhyay Indrajit 
Published: February 2024

The application of lithium-ion batteries is widespread across a variety of sectors, such as portable electronic gadgets, mobile phones, new electric car batteries, and many others. Silicon–Graphene (SiG) anodes are among the sophisticated anode materials that have been used in lithium-ion batteries. These anodes have been widely researched because of their high capacity, strong operating potential, environmental friendliness and great abundance. SiG anodes have shown a lot of promise as a potential anode material for lithium-ion batteries [1]. This is due to the fact that they have solved many issues that were present in Si anodes, including particle pulverization, shedding and failures of electrochemical performance during lithiation and delithiation. Nevertheless, there are still certain issues that need to be improved, such as low initial discharge efficiency, poor conductivity and poor cycle performance. This research focuses on presenting a unique approach that may be used to address the issues associated with Si anode materials. An electrodeposition method that only needs a single unit operation, is applied in the process of constructing composites of SiG from G-1M SiCl4 in [BMIm]Tf2N ionic liquid (IL) [2]. In SiG composites, both silicon and graphene have been seen to have a layered structure (Fig.1 a). The SiG anode displays a specific charge/discharge capacity of 1133/ 2272 mAhg-1 at the first cycle and it drops to 676/ 737 mAhg-1 at the conclusion of 100 cycle at 0.2C (Fig.1b), which demonstrates a robust cycle ability at a moderate rate. The present work will thus discuss on the development of SiG composite by electrochemical method for its utility as negative electrode material in Li ion battery.
References:

Huang, Z. et al. Binder-free graphene/carbon nanotube/silicon hybrid grid as freestanding anode for high capacity lithium ion batteries. Compos. A 84, 386–392 (2016).

Anjali Vanpariya, Kashinath Lellala, Dharini Bhagat, Indrajit Mukhopadhyay*, Electrochemical deposition of Si nano-spheres from water contaminated ionic liquid at room temperature: Structural evolution and growth mechanism, J. Electroanal. Chem., 910 (2022) 116175-116181.

Figure 1
Microstructural Refinement and Surface Modification of Ni-Rich Cathodes for High-Performance Li-Ion Battery
Authors: Kim Myoung-Chan , Hwi Kim , Sun Yang-Kook 
Published: February 2024

Li[Ni1–x–y–zCoxMnyAlz]O2 (NCMA) cathodes have attracted public attention owing to their improved durability by leveraging the advantages of NCM and NCA cathodes. The combination of Mn and Al in a NCMA cathode effectively stabilizes the host layered structure to increase its resistance to microcracking; consequently, NCMA cathodes outperform both NCM and NCA cathodes with the same Ni contents, in terms of cycle life, without sacrificing energy density. However, as the Ni contents of the cathodes exceed 90%, a simple, compositionally engineered NCMA cathode lacks the chemical and mechanical stability to suppress surface degradation and the development of permanent microcracks due to the high incidence of highly reactive Ni4+ species on its surface.1,2 Considering the limitations of NCMA cathodes, a combination strategy involving microstructural engineering to inhibit microcracking, by enabling the efficient dissipation of local strain,3 and the modification of the exposed cathode surface, to protect it against deleterious electrolyte attack, is expected to afford superior Ni-rich layered cathodes.
In this study, we improved the cycling stability of a conventional NCMA cathode with a Ni content of 93% (a NCMA93 cathode) using a combination strategy involving microstructural engineering and surface modification. To this end, we prepared a Sb-doped NCMA93 (denoted as Sb-NCMA93) cathode; Sb was incorporated to refine its microstructure and radially align and elongate its primary particles. Furthermore, we generated a protective F layer on the cathode surface through a chemical reaction between residual lithium compounds and a NH4F coating agent. To comprehensively investigate the synergetic effect of this combination strategy, conventional and Sb-doped NCMA93 cathodes with and without F coatings were synthesized and characterized and their fundamental properties and electrochemical performances compared. Post-mortem analyses were performed to elucidate the origins of the remarkable long-term cycling stability of the optimized cathodes.

Reference
s
:

[1] H.-J. Noh, S. Youn, C. S. Yoon, Y.-K. Sun, J. Power Sources, 2013, 233, 121.
[2] H.-H. Ryu, K.-J. Park, C. S. Yoon, Y.-K. Sun, Chem. Mater. 2018, 30, 1155.
[3] U.-H. Kim, H.-H. Ryu, J.-H. Kim, R. Mücke, P. Kaghazchi, C. S. Yoon, Y.-K. Sun, Adv. Energy Mater.
2019, 9, 1803902.
Investigation of the Solid Electrolyte Interphase of Silicon Wafers Using a Fluorine-Free Electrolyte
Authors: Patranika Tamara , Edström Kristina , Hernández Guiomar 
Published: February 2024

Lithium-ion (Li-ion) batteries have become an important solution for energy storage owing to their high gravimetric and volumetric energy density. The electrolyte solution of the battery has a large effect on the stability and performance of the cell. During the first cycles of a battery, the solid electrolyte interphase (SEI) layer is formed due to the degradation of the electrolyte. Hence the composition of this layer, and the stability, are dependent on the electrolyte composition.
The most commonly used electrolyte for Li-ion batteries is the salt lithium hexafluorophosphate LiPF6 dissolved in organic solvents together with additives, both containing fluorinated compounds.1 However these fluorinated compounds are susceptible to release HF which is toxic and corrosive which could be detrimental for the cell performance but also hinder the recycling process. Therefore, fluorine-free electrolytes could be a promising alternative. While this type of electrolytes has been investigated with graphite anodes, when moving to higher energy densities, such as silicon, their performance and degradation mechanism is not yet clear.2

Previous research has shown increased stability for Li-ion batteries using a fluorine-free electrolyte based on the salt lithium bis(oxalato) borate (LiBOB).2 Furthermore, operando X-ray reflectometry (XRR) measurements on silicon wafers half-cells with the same electrolyte have shown the build-up of multiple layers on the anode, providing the thicknesses and densities of the different layers. This work presents the chemical composition of these different layers formed on the silicon wafers at different potentials when using a fluorine-free electrolyte based on LiBOB in ethylene carbonate and methyl ethyl carbonate. These results are also compared with the effect of adding vinylene carbonate VC as an additive. The different components in these layers are correlated to the previous XRR data to explain the SEI-formation mechanism with fluorine-free electrolytes.

Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem Rev
104, (2004).

Hernández, G. et al. Elimination of fluorination: The influence of fluorine-free electrolytes on the performance of LiNi1/3Mn1/3Co1/3O2/silicon-graphite li-ion battery cells. ACS Sustain Chem Eng
8, (2020).
Liovix® Printable Lithium Technology for Controlled and Scalable Prelithiation of Silicon Anodes
Authors: Fitch Brian , Yakovleva Marina , Xia Jian 
Published: February 2024

Loss of active lithium in the first cycle permanently lowers the lithium-ion cell energy density. Prelithiation employs an external, sacrificial source of lithium to offset these losses allowing more efficient use of lithium from the cathode and raising the cell energy density.
LIOVIX®printable lithium technology is comprised of stabilized lithium metal powder (SLMP®) dispersed in a compatible solvent along with other rheology and performance modifiers to create a formulation that is chemically stable and not prone to separation for extended periods of time. The technology is easily scalable using industry standard coating and printing equipment to apply the formulation to the surface of a prefabricated anode. LIOVIX® can be used in anodes with a range of silicon content, because lithium loading can be accurately controlled based on the applications’ requirements.
In this presentation, we will compare LIOVIX® to other prelithiation methods. The electrochemical results will be discussed as well.
Influence from Mechanical Stress on State of Health of Large Prismatic Lithium-Ion-Cells Under Various Temperatures
Authors: Petursdóttir Erla , Kohlhuber Markus , Ehrenberg Helmut 
Published: February 2024

Volume expansion of lithium-ion cells is a well-known ageing phenomenon, in which the outer and inner geometry of the cell is subject to deformation due to physicochemical reactions during ageing and operation, resulting in corresponding degradation effects such as loss of capacity and higher internal resistance in the cell. In a cell module the external deformation of the cells poses a major challenge to the mechanical design due to the resulting swelling forces.
In this work, compression force and thickness measurements were performed on large prismatic lithium-ion cell with various compression magnitudes to quantify the influence of mechanical stress on state of health of the cells. The impact of the bracing is shown for lithium-ion cells cycled with 1C constant current constant voltage charge and 1C constant current discharge up to 500 cycles with 100% depth of discharge and at every 50 cycles, the capacity of the cells was determined, and electrochemical impedance spectroscopy measurements were conducted. The cells were cycled until the threshold of 80 % state of health was reached. In-situ thickness measurements showed cell expansion during charging and contraction during discharging due to lithiation as well as de-lithiation additionally the measurements showed an irreversible thickness change in the cell due to ageing phenomenon. To quantify the increase in internal resistance a distribution of relaxation time (DRT) analysis was performed on the electrochemical impedance spectroscopy (EIS) data.
Harmonization of Testing Procedures for All Solid State Batteries
Authors: Lee Yan Ying , Weber Andre 
Published: February 2024

All Solid State Batteries (ASSBs) with lithium-ion based conducting solid state electrolytes are considered the next generation high performance batteries. They enable high power densities due to their single ion conducting solid electrolyte, eliminating salt concentration gradients and related polarization losses in the cell, and ensuring an unrivalled level of safety due to their non-combustibility. Currently, a variety of ASSBs based on different solid state electrolytes such as polymers, thiophosphates, oxides and combinations thereof are being developed.
One general problem with ASSBs is establishing and maintaining contact between the solid electrolyte and the active material phase during production and cycling, respectively. In conventional lithium-ion batteries (LiBs), this contact is ensured by the liquid state of the electrolyte, but in ASSBs, chemical expansion and contraction of the active material during lithiation and delithiation can detach this contact, resulting in decreased capacity due to the loss of active material. As a consequence, ASSBs are often operated under pressurized conditions, applying pressures significantly exceeding those in conventional LiBs. The same holds for the operating temperature window. Especially for polymer electrolyte-based ASSBs, they are often operated at higher temperatures to compensate for the low ionic conductivity of polymers at room temperature. With respect to cell testing, such operating requirements must be considered, and testing protocols are designed according to the individual requirements of the tested cell.
This contribution aims to provide an overview of testing protocols for various types of ASSBs applied to different cells with polymer-, thiophosphate-, oxide-, and hybrid-electrolytes. These protocols will be compared with standardized testing routines for conventional LiBs. Based on this compilation, a harmonized testing procedure that covers the special requirements of the individual cell types and enables a fair comparison of different ASSBs is suggested. Additionally, examples of ASSB testing results will be discussed, taking into consideration the harmonization of different testing parameters.
Improving Lithium-Ion Batteries By Replacing Polyethylene Terephthalate Jellyroll Tape
Authors: Adamson Anu , Bötticher Tom , Tuul Kenneth , Garayt Matthew D. L. , Azam Saad , Metzger Michael 
Published: February 2024

Every lithium-ion battery cell produced today that is either wound or stacked contains tape. This tape serves the mechanical purpose of holding together the wound jellyroll or stacked electrodes before inserting it into the cell casing, after which the tape serves no purpose. Battery manufacturers often test inactive cell parts for their physical parameters, i.e., elongation, water absorption, and temperature resistance.1 However, their chemical stability is often overlooked. Recently, it was demonstrated that polyethylene terephthalate (PET) tape can partially dissolve in the harsh lithium-ion battery cell chemistry into its monomer dimethyl terephthalate (DMT). This molecule can act as an unwanted redox shuttle in LFP/graphite or NMC811/graphite cells, inducing self-discharge of the battery.2

Figure 1 shows Fourier-transform infrared (FTIR) spectra of tapes obtained from discarded cellphone batteries. Many well-known lithium-ion battery producers use PET tape in their products. In addition, the FTIR spectra show that after the cells have been cycled, the surface layer of these tapes is severely corroded. This study will show open circuit storage, Ultra-High Precision Coulometry, and long-term cycling results from LFP/graphite cells with PET tape. The study will also show how swapping PET tape for a more stable alternative can significantly improve the performance and reduce the self-discharge of LFP/graphite pouch cells.
Figure caption:

Figure
1
. FTIR spectra of jellyroll closing tapes (a) extracted from discarded cellphone batteries (b).
References:

E. Foreman et al., Adv. Sustainable Syst., 1, 1700061 (2017).

S. Buechele et al., J. Electrochem. Soc., 170, 010511 (2023).

Figure 1
Unraveling the Lithium Storage Mechanism at Low Potentials in Niobium Pentoxide Anodes for Lithium-Ion Batteries
Authors: Xue Xilai , Asenbauer Jakob , Eisenmann Tobias , Dinda Sirshendu , Lepore Giovanni Orazio , Xing Silin , Mullaliu Angelo , Diemant Thomas , d'Acapito Francesco , Parac-Vogt Tatjana N. , Fichtner Maximilian , Tübke Jens , Bresser Dominic 
Published: February 2024

State-of-the-art lithium-ion anodes based on graphite exhibits high specific capacity and a low de-/lithiation potential, thus, enabling very high energy densities at full-cell level. However, the rather sluggish lithiation kinetics render them less suitable for fast-charging batteries[1]. A potential alternative that has gathered increasing interest in recent years is Nb2O5, but the commonly employed lower cut-off voltage of 1.0 V vs. Li+/Li in combination with the lower capacity compared to graphite limit the achievable energy density[2,3].
Herein, the extended lithiation to lower cut-off voltages is reported, resulting in increased capacities while maintaining a very stable cycle life. Remarkably, this behavior is generally independent from the initial polymorph, and both monoclinic and orthorhombic Nb2O5 show a substantial increase in capacity for several hundred cycles. To elucidate the underlying storage mechanism, comprehensive characterization via operando/ex-situ X-ray diffraction (XRD), operando Raman spectroscopy, operando isothermal microcalorimetry (IMC), ex-situ X-ray absorption spectroscopy (XAS), and ex-situ X-ray photoelectron spectroscopy (XPS) was conducted. It appears that the occurrence of an additional phase transition at low potentials plays a decisive role for the enhanced capacity and superior cycling stability.

Reference

[1] J. Asenbauer, T. Eisenmann, M. Kuenzel, A. Kazzazi, Z. Chen, D. Bresser, Sustain. Energy Fuels
2020, 4, 5387–5416.
[2] P. Jing, K. Liu, L. Soule, J. Wang, T. Li, B. Zhao, M. Liu, Nano Energy
2021, 89, 106398.
[3] T. Li, G. Nam, K. Liu, J. H. Wang, B. Zhao, Y. Ding, L. Soule, M. Avdeev, Z. Luo, W. Zhang, T. Yuan, P. Jing, M. G. Kim, Y. Song, M. Liu, Energy Environ.
Sci.
2022, 15, 254–264.
Cleaning up Operando Battery X-Ray Diffraction with Total Scattering Computed Tomography
Authors: Wragg David Stephen 
Published: February 2024

Operando X-ray diffraction (XRD) and total scattering investigations of battery electrode materials allow us to relate structure and electrochemical properties down to the atomic level. By studying the materials under real working conditions without allowing the materials to relax or react outside the battery, we obtain the most reliable possible structural information. Unfortunately, in most operando experiments, even when we use heavily modified cells to remove barriers to our probe radiation, the signal from the material of interest is significantly obscured by contributions from other battery components. The problems are increased when we seek to study electrode materials which either are, or become, amorphous during battery cycling: removing non-sample contributions is an essential part of pre-processing total scattering data for pair distribution function (PDF) analysis, which can reveal the local structures of non-crystalline materials.
To address these problems, we have developed operando total scattering computed tomography (TSCT) as a method for obtaining clean, 5-dimensional (3-D space, time, and chemical structure) information on working batteries. The method allows us to select specific areas of the active electrode and obtain XRD and PDF information without any contributions from other components of the battery. The high-quality of the resulting data has allowed us to understand the cycling mechanisms of poorly scattering, amorphous, alloying anode materials (sodium cycling in phosphorus)[1], and complex, multi component, conversion-alloying systems (lithium cycling in bismuth vanadate)[2]. While the first example mainly uses the focusing power of TSCT to obtain the best possible data, the latter case uses the spatial resolution of the data to identify signs of a longer-term deactivation mechanism based on agglomeration of the nanoclusters of active material during repeated cycling. Further studies are currently in progress to apply the method to other difficult anode systems including silicon.
[1] J. Sottmann, M. Di Michiel, H. Fjellvåg, L. Malavasi, S. Margadonna, P. Vajeeston, G.B.M. Vaughan, D.S. Wragg, Chemical Structures of Specific Sodium Ion Battery Components Determined by Operando Pair Distribution Function and X-ray Diffraction Computed Tomography, Angew. Chem. Int. Ed. 56, pp. 11385-11389, 2017
[2] J. Sottmann, A. Ruud, Ø.S. Fjellvåg, G.B.M. Vaughan, M. Di Michel, H. Fjellvåg, O.I. Lebedev, P. Vajeeston, D.S. Wragg, 5D total scattering computed tomography reveals the full reaction mechanism of a bismuth vanadate lithium ion battery anode, Phys. Chem. Chem. Phys. 24, pp.27075-27085, 2022

Figure 1