bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Magnetic Field Assisted Electrodeposition of Topographically and Chemically Structured Copper-Nickel Deposits
Authors: Tschulik Kristina , Gerwin Maximilian , Jlailati Zaher 
Published: February 2024

Electrodeposition under the influence of magnetic field has sparked the interest of researchers for decades. The beneficial effects of homogenous magnetic fields on electrodeposition enable increased deposition rates as well as smoother deposits.[1] These effects have been intensively studied and attributed to magnetohydrodynamic forces. Conversely, several questions remain unanswered with respect to the beneficial influence of heterogeneous magnetic fields.[2] There, local convection allows structuring of deposit morphologies; however, it has not yet been reported if magnetic gradients can be used to induce local compositional changes.[3] Here, we investigate the opportunity to induce both, topographic and chemical structuring of electrodeposits by magnetic gradients.
For this purpose, potentiostatic deposition of CuNi films is carried out on an Au coated glass slide using a sulphate-based aqueous electrolyte. An iron wire template is magnetised by a permanent magnet and placed below the working electrode to apply well defined, high magnetic gradients during electrodeposition. The obtained Cu-Ni deposits are analysed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The results of these measurements reveal that the deposited film topography follows the distribution of superimposed magnet field gradients and that a local compositional change of the deposits is possible. Thus, our results open up a new path to control the local morphology of complex deposits structures and other properties of films by magnetic gradient assisted electrodeposition.

References

(1) Uhlemann, M.; Tschulik, K.; Gebert, A.; Mutschke, G.; Fröhlich, J.; Bund, A.; Yang, X.;
Eckert, K. Eur. Phys. J. Spec. Top. 2013, 220, 287–302.
(2) Mutschke, G.; Tschulik, K.; Weier, T.; Uhlemann, M.; Bund, A.; Fröhlich, J.
Electrochimica Acta 2010, 55, 9060–9066.
(3) Karnbach, F.; Uhlemann, M.; Gebert, A.; Eckert, J.; Tschulik, K. Electrochimica Acta
2014, 123, 477–484
Cost-Effective Milled Silicon and Exfoliated Graphene Anode for High-Performance Li-Ion Batteries
Authors: Aziz Mohammad Abdul , Joo Yong Lak , Gao Ziang 
Published: February 2024

Lithium-ion batteries play a significant role in modern electronics and electric vehicles. However, current lithium-ion battery chemistries are unable to satisfy the increasingly heightened expectations regarding energy demand and reliability. To boost the overall energy density while ensuring the safety of Li batteries, researchers have focused on developing the battery materials [1]. Silicon has an ultrahigh theoretical capacity and has been regarded as the best choice for next-generation lithium-ion battery anodes, but it also suffers from dramatic expansion during cycling [2]. Hence mitigating volume expansion is one of the main challenges towards developing a successful Si based anodes. Herein, a facile air-controlled electrospray method to directly deposit silicon/graphene (Si/Gr) onto current collectors was described. This method is inspired by an electrospinning process and possesses all the advantages that electrospinning has such as low cost, easy scaling up, and simultaneous solvent evaporation during the spraying process. Cost-effective silicon/graphene (Si/Gr) composite electrodes have been investigated for the multiple benefits of Gr in providing mechanical integrity to buffer the silicon volume expansion while maintaining electronic contact with Si to provide a Li-ion transport pathway and to form a uniform solid electrolyte interface (SEI) layer. Our results revealed a superior battery performance including a capacity of 1000 mAh/g at 2C rates and minor capacity loss during long cycling. The details of synthesis, characterization, and lithium-ion battery results of the hybrid anodes will be presented.

References

[1] Li et al., Adv. Energy Mater., 2021, 11, 2003239.
[2] Guo et al., Adv. Funct. Mater., 2021, 31, 2102546.
Pre-Lithiation of Silicon-Based Anode Materials: Concepts and Realization
Authors: Kolesnikov Aleksei , Profanter Laurin , Lee Ilha , Haneke Lukas , Winter Martin , Kasnatscheew Johannes 
Published: February 2024

The capacity in lithium ion battery (LIB) relies on active lithium, i.e., lithium-ions and electrons, which separately shuttle between the electrodes during charge and discharge. Given state-of-the art active materials for anodes, loss of active lithium and capacity remains a major challenge during LIB operation, in particular in the first charge/discharge cycle due to electrolyte decomposition and formation of solid electrolyte interphase (SEI).
Pre-lithiation, i.e., artificial increase in active lithium amount into the battery is a promising strategy to counteract active lithium loss. Electrochemical(1) and chemical(2,3) methods of pre-lithiation can be distinguished. While electrochemical methods are based on the use of an external power source, the driving force of the chemical reaction is a negative change in the Gibb´s free energy which in the case of pre-lithiation is provided by the use of highly reactive chemical compounds (e.g. lithium-organic complex solutions or lithium metal). The use of lithium metal allows for a wide range of technological processes, including lamination of lithium foil, gas-phase deposition, application of lithium melts or suspensions containing lithium powder. In this contribution, various concepts of pre-lithiation will be discussed from experimental and up-scaling point of view on the example of Si-based anodes.
(1) Haneke, L.; Pfeiffer, F.; Bärmann, P.; Wrogemann, J.; Peschel, C.; Neumann, J.; Kux, F.; Nowak, S.; Winter, M.; Placke, T., Insights into Electrolytic Pre‐Lithiation: A Thorough Analysis Using Silicon Thin Film Anodes. Small
2022, 2206092.
(2) Adhitama, E.; Bela, M. M.; Demelash, F.; Stan, M. C.; Winter, M.; Gomez‐Martin, A.; Placke, T., On the Practical Applicability of the Li Metal‐Based Thermal Evaporation Prelithiation Technique on Si Anodes for Lithium Ion Batteries. Advanced Energy Materials
2023,
13 (3), 2203256.
(3) Bärmann, P.; Mohrhardt, M.; Frerichs, J. E.; Helling, M.; Kolesnikov, A.; Klabunde, S.; Nowak, S.; Hansen, M. R.; Winter, M.; Placke, T., Mechanistic Insights into the Pre‐Lithiation of Silicon/Graphite Negative Electrodes in “Dry State” and After Electrolyte Addition Using Passivated Lithium Metal Powder. Advanced Energy Materials
2021,
11 (25), 2100925.
Understanding the Influences of Laser Perforation on Thick Electrodes for Lithium Ion Batteries Via 3D Microstructure Simulations
Authors: Krumbein Lukas , Hein Simon , Danner Timo , Prifling Benedikt , Neumann Matthias , Kouli Maher , Mund Malte , Schmidt Volker , Latz Arnulf 
Published: February 2024

Laser perforation is a precise technique to decrease ionic diffusion limitations by selectively removing material with spatial precisions of tenth of micrometres. It is mainly applied in thick electrodes to improve foremost rate capability, as well as cycle stability, Li plating detention and wetting efficiency.[1] [2]
Mostly, holes are created in the batteries through-direction leading to a material removal of about 5%-10% of the initial load. This removal creates inhomogeneous diffusion channels especially into layers close to the current collector, as opposed to a homogeneous increase in porosity.
It is of interest to find an optimal trade-off between the competing factors of capacity loss and increase in ion conductivity due to material ablation. Optimization of structuring parameters requires intimate knowledge of electrode and material properties. However, there is a lack of an adequate description of the inhomogeneous structure and its influence on the electrochemical performance. [1]
In our presentation we show a detailed 3D microstructure resolved simulation study, examining the influencing parameters for laser perforation.
The data suggests, that perforating holes with small diameter at a short distance, which results in an ablation of ca. 8% gives generally desirable improvements for the rate capability. Laser perforation is distinctively favourable in contrast to a raise in homogenous porosity.
Moreover, the microstructure resolved simulation also allows for a detailed analysis of different hole shapes and hole misalignment in electrodes after stacking. We evaluate the impact of different configurations on the electro chemical performance. [3]
References:
[1] Dunlap et. al., JPowSour, 2022, 231464
[2] Chen et. al., JPowSour, 2020, 228475
[3] De-Lauri et. al., ACSAEM, 2021, 4, 13847-13859

Figure 1
Frequency Response Informed Order Reduction Approaches for Pseudo-2D Model for Li-Ion Batteries
Authors: Mishra Astitva , Jangale Akash Suhas , Subramanian Venkat R. , Suthar BharatKumar 
Published: February 2024

To simulate the battery performance quickly using the P2D model,1,2 various simplifications and mathematical reformulations are introduced. One such simplification is the polynomial profile approximation in the solid phase. Such simplifications result in a significant reduction in the simulation time while having a minor compromise in the accuracy, especially for highly fluctuating currents. Building on the previous work by Subramanian et al.,3,4 in this presentation, the Hexic profile polynomial approximations are proposed. The frequency response-based criteria were used to derive the optimal coefficients which give rise to the best possible Hexic model for a given family of current profiles.5

Compare to the Quartic model (QP) based simplifications, the proposed Hexic model (HP) provides comparable computational time (t
sim) but offers a factor of 3 improvements in the average error in the cell voltage calculation (εavg [mV]). However, compared to the fully converged FD model, it offers significant improvement in computational time at the cost of 0.5 mV average error in the cell voltage (see Figure 1).
In the context of the P2D model, Hexic profile-based solid phase concentration treatment leads to much better prediction (compared to the parabolic and quartic profiles) of the internal variables such as current distribution in electrodes and the stress distribution (radial and tangential stresses inside the solid particles) generated during lithiation and de-lithiation process.
The presentation will also discuss critical comparison between the global polynomial-based models (orthogonal collocation and Galerkin approaches) and the frequency domain-based approaches.
References

Doyle, T. F. Fuller, and J. Newman, J Electrochem Soc, 140, 1526 (1993).

Newman and K. E. Thomas-Aleya, John Wiley & Sons, New Jersey (1991).

R. Subramanian, J. A. Ritter, and R. E. White, J Electrochem Soc, 148, E444 (2001).

R. Subramanian, V. D. Diwakar, and D. Tapriyal, J Electrochem Soc, 152, A2002 (2005).

Mishra, V. R. Subramanian and B. Suthar, J Electrochem Soc, 169 (12), 120532 (2022).

Figure 1
Simulation Study of Li-Ion Batteries Considering the Porosity and Tortuosity of Separator
Authors: Permatasari Agnesia , So Magnus , Mori Yuki , Saito Yuki , Inoue Gen 
Published: February 2024

Lithium-ion batteries (Li-ion batteries) offer high energy and power densities, making them the most widely used battery technology for energy storage in various applications such as grid-scale, automotive, and electronic devices. One of the critical components of a Li-ion battery is the porous separator which can impair performance at high charge/discharge rates. Separator has a considerable influence on the transport of lithium ions. The structural properties of the separator, such as porosity and tortuosity can have a significant impact on heat generation and polarization of lithium concentration as well as the current density distribution inside the separator. The porosity of a porous separator is a well-defined feature that may be easily determined. In contrast, the tortuosity of separators, is more difficult to assess.
To model and calculate the separator properties, in this study, the simulated structural separator was constructed by numerical analysis1 based on actual separator structure from Cryo-FIB-SEM. The numerical simulation of the ion-transport model for concentrated electrolyte solutions using the model developed by Newman et al2. Different structures of separators provided different behaviors at different charge/discharge rates. To evaluate overall battery performance, using the previously reported structural information3,4, lithium nickel manganese cobalt oxides (NCM), 1.0 M LiPF6 solution in EC-DEC solvent, and graphite were used for the cathode, electrolyte, and anode, respectively.
This work simulated and compared three different separator structures: foam, non-woven fabric, and stretched structure with three different constant charging rate (C-rate) conditions (1 C, 5 C and 8 C). The calculation of porosity and tortuosity has been done for through-plane model. The higher C-rate will increase the heat generation significantly and affect the battery`s thermal behavior. The tortuosity and porosity have correlation on the effective ionic conductivity σeff = (ε/τ)*σ and effective diffusion coefficient Deff = (ε/τ)*D. Higher separator porosity can effectively increase the effective diffusion coefficient, hence improving mass transfer and reducing resistance. The separator with uniform porosity and smaller tortuosity showed smaller diffusion polarization because Li+ can be transported easily and uniformly in it, leading to lower heat generation even in high C-rate condition. The model developed in this study is intended to be valuable in understanding behavior of porous separators and optimizing the battery design.
Acknowledgement: This research was carried out under the project (Grant Number JPMJMI21G4) supported by the JST-Mirai Program, Japan.
References:

Inoue et al., J. Pow. Sour.,
175, 145 (2008).

Newman and K. Thomas-Alyea, Electrochemical Systems, 3rd ed., Wiley Interscience, Hoboken, (2004).

Inoue et al., J. Chem. Eng. Japan.,
54 (5) 207-212 (2021).

K. Ikeshita et al., ECS Trans.,
75 (20) 165-172 (2017).
Modeling of Crystal Structure in Li-Rich Layered Oxides for Rechargeable Lithium Cells
Authors: Celeste Arcangelo , Tuccillo Mariarosaria , Silvestri Laura , Brutti Sergio 
Published: February 2024

Lithium-Ion Batteries (LIBs) require further development in terms of safety and performance to establish also in the automotive market and new materials at both electrode sides as well as at the electrolyte side are necessary to overcome the state of-the-art and the commercial benchmarks. [1] The positive electrode materials constitute the bottleneck for present LIBs. They are based on layered structures (LiCoO2, NMC, NMA), spinel (LiMn2O4) and olivine LiFePO4, with rather moderate specific capacities (120–180 mAhg−1). [2] Therefore, the resulting specific energies are insufficient to meet market demand. Over-stoichiometric Li-rich layered oxides (LRLOs) are a family of positive electrode materials with promising theoretical electrochemical performance. [3] Indeed, they have received widespread attention due to their extremely high specific capacity (>250 mAhg−1) and low cost. Their extraordinary capacity has been confirmed to originate not only from the redox activities of transition metals, but also from the redox activities of oxygen anions. The crystal structure of LRLOs is an open playground of debate. There are two main hypotheses: a) a two phase nano-domain and b) a single phase solid solution. In this framework, the modeling of the crystal structure is quite challenging. Usually, the description of the structure of LRLOs can be done with rhombohedral or monoclinic unit cell. Nevertheless, the use of convention unit cells leads to a bad representation of the crystal structure because of the missing of structure features in the superstructure region (20<θ<30 in typical diffraction pattern with Cu Kα). In this communication, we demonstrate that extensive defectivities play a key role in the shape and intensity of diffractograms of LRLOs. In particular, we show how the use of supercells or defects (antisite defects and stacking faults) can help in the description of crystal structure of this class of materials.
[1] Zubi, G.; Dufo-López, R.; Carvalho, M.; Pasaoglu, G. The Lithium-Ion Battery: State of the Art and Future Perspectives. Renewable and Sustainable Energy Reviews 2018, 89, 292–308.
[2] Casas-Cabanas, M.; Ponrouch, A.; Palacín, M.R. Blended Positive Electrodes for Li-Ion Batteries: From Empiricism to Rational Design. Isr J Chem 2021, 61, 26–37.
[3] Nie, L.; Chen, S.; Liu, W. Challenges and Strategies of Lithium-Rich Layered Oxides for Li-Ion Batteries. Nano Res 2022.
Bayesian Approach to Estimate Distribution of Relaxation Times for Lithium-Ion Batteries
Authors: Kim Seongyoon , Choi Jung-Il 
Published: February 2024

Electrochemical impedance spectroscopy (EIS) has emerged as a powerful tool for analyzing the state of lithium-ion batteries due to its ability to provide rich electrochemical information. Traditionally, equivalent circuit and physical models have been utilized for interpreting EIS data. However, these methods possess inherent drawbacks: equivalent circuit models are non-unique, while physical models can be challenging to implement. As an alternative, the distribution of relaxation times (DRT) has garnered increasing attention in recent years. The DRT method enables the analysis of EIS data without predefining a model's shape, allowing for the decomposition of internal characteristics in complex systems, such as lithium-ion batteries. Despite its advantages, DRT estimation is an ill-posed inverse problem that often requires regularization or fine-tuning based on empirical choices, which can lead to the misinterpretation of EIS data.
To address these challenges, we propose a Bayesian approach that enables the estimation of DRT while considering uncertainties, even in the presence of observational errors in EIS data. Moreover, the proposed method can assist in estimating the state of health (SOH) of the battery, which provides valuable insights into the battery's overall performance, longevity, and safety. To validate the efficacy of our proposed method, we apply it to synthetic EIS data and compare its performance with existing DRT estimation methods. The results show that the proposed Bayesian approach offers a more robust and accurate estimation of DRT. We also demonstrate the practical applicability of the proposed method by applying it to real lithium-ion battery EIS experimental data, where it successfully extracts meaningful information about the battery's internal state and SOH. In summary, the proposed DRT-based Bayesian method has the potential to enable a robust diagnosis of the internal state and SOH of lithium-ion batteries through EIS measurements. By incorporating this approach, researchers and industry practitioners can gain a deeper understanding of battery performance, facilitating the development of improved diagnostic techniques and battery management strategies to enhance the performance and reliability of lithium-ion batteries. This, in turn, could contribute to the broader adoption of sustainable energy solutions, such as electric vehicles and renewable energy storage systems.
This work was supported by the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grants funded by the Ministry of Trade, Industry & Energy, Republic of Korea (No. 20214910100070).

Figure 1
Ageing and Post-Mortem Study of LNMO-Based Lithium Ion Battery Pouch Cells
Authors: Schmitt Christina , Maximillian Davin , Sotta Dane , Martin Agathe , Debruyne Cédric , Reynier Yvan , Buga Mihaela , Ungureanu Cosmin , Kopljar Dennis , Friedrich K. Andreas 
Published: February 2024

Lithium ion batteries are nowadays widely employed in a variety of applications from consumer electronics to electric vehicles. Due to the rising demand for batteries, more affordable and sustainable batteries are needed that exhibit at the same time high energy densities, high power capabilities, long cycle life, and increased safety. One concept to meet these requirements is to develop cobalt-free cathode materials of which the high-voltage spinel LNMO (LiNi0.5Mn1.5O4) is a promising material due to its high energy density and high operating voltage of 4.7 V. However, the high operating voltage has also its drawbacks. Commonly used carbonate-based electrolytes oxidize at high voltages, leading to the continuous formation of a cathode-electrolyte interface (CEI). Additionally, LNMO is prone to transition metal dissolution which not only leads to a reduced stability of the cathode active material but due to migration and deposition of the transition metals on the anode surface also to an altered solid electrolyte interface (SEI) formation and significant impedance rise of the anode.1 Both ageing mechanisms provoke increased lithium loss and high resistances and thus a poor cycling performance.2, 3

In the Horizon 2020 LC-BAT5 project HYDRA, LNMO-based prototype pouch cells are developed and built. Herein, we want to present the results from the comprehensive analysis of their performance and cycling behavior. The influence of upper cut-off voltage, charge and discharge current rate as well as temperature on the degradation are thoroughly investigated by electrochemical methods such as differential voltage analysis and impedance spectroscopy. After cycling, selected cells are opened under argon atmosphere followed by electrochemical characterization as well as physical analysis such as SEM-EDX and XPS in order to get further insights into the underlying ageing mechanisms. We thereby reveal the main degradation mechanisms as a function of the cycling conditions and derive solutions on how to increase the cycle life.
1. C. Zhan, T. Wu, J. Lu and K. Amine, Energy Environ. Sci.,11 (2), 243-257 (2018).
2. J. Ma, P. Hu, G. Cui and L. Chen, Chem. Mater.,28 (11), 3578-3606 (2016).
3. W. Li, Y.-G. Cho, W. Yao, Y. Li, A. Cronk, R. Shimizu, M. A. Schroeder, Y. Fu, F. Zou, V. Battaglia, A. Manthiram, M. Zhang and Y. S. Meng, J. Power Sources,473, (2020).
Pseudo-OCV (a) and differential voltage analysis curves (b) of LNMO-graphite pouch cell cycled with 0.3C CCCV charge and 0.1C discharge at 25°C

Figure 1