bluuebunny/crossref_metadata_2025_split huggingface dataset:
Lithium Ion Battery Electrolytes Based on Deep Eutectic Solvents
Authors: Elgammal Ramez Ahmed , Fraenza Carla Cecilia , Zawodzinski Thomas A. , Greenbaum Steven 
Published: September 2023

Deep eutectic solvents (DESs) have emerged as an alternative to both common organic solvents and ionic liquids (ILs). DESs share physicochemical properties with ILs such as low vapor pressure, high thermal stability, while offering advantages such as low toxicity, lower cost, and ease of preparation. Moreover, DESs are attractive candidates for electrochemical applications due to their large voltage windows and solubility properties. DESs as a solvent class share a general composition of a hydrogen bond donor (HBD), typically a polyol, amide, or acid, and a hydrogen bond acceptor (HBA), usually a quaternary ammonium or phosphonium salt. At a specific molar composition of a HBD and HBA, the DES forms a eutectic mixture resulting in a large melting point depression.
Despite being widely studied, the microscopic structures of DESs have remained largely uncharacterized. Herein, we present a multitechnique NMR study of ethaline (ethylene glycol + choline chloride). Pulsed field gradient diffusion, nuclear Overhauser effect spectroscopy (NOESY), 13C NMR relaxation experiments are deployed to sample a range of frequencies and modes of motion of the polyol and choline components of the DES. Generally, translational and rotational diffusion of polyols are more rapid than those of choline while short-range rotational motions observed from 13C relaxation indicate slow local motion of ethylene glycol at low choline chloride (ChCl) content.
Additionally, we have investigated the solubility properties of several lithium salts (LiTFSI, LiFSI, LiBF4, and LiOAc) in these DESs and utilized the same suite of NMR techniques to understand how they act as solvents. One interesting observation is that the Li+ diffusivity exceeds that of the counterion for TFSI-, but not for FSI-. Finally, large changes in the structural organization of DESs that result from the presence of lithium salts may serve as a guide to the design of a new class of electrolytes for lithium-ion batteries.
(Invited) High-Throughput Development of LiCoPO4
Authors: Zeinali Galabi Nooshin , Jia Shipeng , Jonderian Antranik , Yoon Gabin , MA Sang Bok , McCalla Eric 
Published: September 2023

High voltage cathodes are attractive for high energy density Li-ion batteries, particularly with the innovation of solid electrolytes with large stability windows. However, candidates such as LiCoPO4 have presented numerous problems due to poor electronic/ionic conductivities. Typical solutions involving nanosizing result in extremely poor cycling performance. Herein, we first apply high-throughput methods to develop near-micron sized carbon-coated LiCoPO4 with improved energy density and capacity retention.1 In total, 1300 materials with 46 different substituents were synthesized and characterized. A number of substituents showed greatly improved capacity (e.g. 160 mAh/g for 1% In substitution vs. 95 mAh/g for the pristine). However, co-doping was required to improve extended cycling. Li1-3xCo1-2xInxMoxPO4 was found to be particularly effective with dramatically improved cycling (as high as 100 % after 10 cycles, vs. ~50 % in unsubstituted). While In improved the electronic conductivity of the carbon-coated materials, Mo co-doping gave larger particles and DFT calculations showed that Mo impedes the formation of Li/Co antisite defects.
While the above described experiments were solely guided by the researchers intuition, we also explore potential benefits of using machine-learning (ML) algorithms to guide the composition exploration. Random compositions were first prepared to supplement our existing data as part of the training set, then further synthesis was performed based on the ML outputs. The results will be presented in detail to help establish to what extent ML can be used to further leverage our group's high-throughput data.

References

1. A. Jonderian, S. Jia, G. Yoon, V.T. Cozea, N. Zeinali Galabi, S.B. Ma, and E. McCalla. Accelerated Development of High Voltage Li-Ion Cathodes. Adv. Energy Mater. 2022, 12, 2201704.
Studying the Mechanics of NMC Cathode Particles for Direct Battery Recycling
Authors: Preimesberger Juliane Irine , Coyle Jaclyn 
Published: September 2023

As the global usage of lithium-ion batteries skyrockets, there is increasing interest in recycling spent batteries. While the economic and environmental impacts of reclaiming high-value elements such as cobalt, nickel, and lithium are obvious, directly-recycling cathode materials takes this one step further by both recovering these elements as well as preserving particle structure, which takes significant processing cost and materials to manufacture. Previous literature has found a correlation between mechanical strength and cyclability of cathode materials, indicating that restoring the structural integrity of active particles is crucial to direct recycling efforts [1, 2]. Cathode materials experience significant fracture and cracking during the lifetime of a battery, caused by both the calendering process during formation and the volume expansion of the particles upon lithium insertion during cycling [1]. Many recycling processes rely on high-temperature annealing to repair cracks in end-of-life cathode particles. As fracture due to calendering exists in pristine electrodes, it is possible that the annealing step does not need to heal all cracks in end-of-life material to match pristine electrode performance. To lower recycling costs, it is vital that the requirements for the annealing step are well understood.
To address this, we characterize the mechanical strength of nickel manganese cobalt (NMC) cathode particles at pristine, end-of-life, and recycled-annealed states. We leverage multiple experimental techniques, including bulk compressive testing, nanoindentation, and nano-CT measurements, to characterize the particles’ bulk modulus, Weibull distribution, and fracture toughness, among others, and correlate these mechanical properties to cycling performance. From this, we provide insight into an optimal annealing step that minimizes cost without sacrificing recycled material mechanical and electrochemical quality.
References:
[1] I. Hamam, R. Omessi, D. Rathore, C. Geng, R. Cooke, K. Plucknett, D. P. Bishop, N. Zaker, G. A. Botton, C. Yang and J. R. Dahn, "Correlating the mechanical strength of positive electrode particles to their capacity retention," Cell Reports Physical Science, vol. 3, no. 100714, 2022.
[2] R. Xu, H. Sun, L. S. de Vasconcelos and K. Zhao, "Mechanical and Structural Degradation of LiNixMnyCozO2 Cathode in Li-Ion Batteries: An Experimental Study," Journal of The Electrochemical Society, vol. 164, no. 13, pp. A3333-A3341, 2017.
The Effect of Carbon Type and Solvent/Binder Ratio on the Structure and Performance of Sulfur Cathodes in Lithium-Sulfur Batteries
Authors: Lateef Saheed Adewale , Manjum Marjanul , Chmiola John , Albano Fabio , Mustain William Earl , Jalilvand Golareh 
Published: September 2023

Lithium-Sulfur (Li-S) batteries are among the popular candidates for next-generation rechargeable energy storage devices due to their high specific capacity and superior energy storage capabilities. However, commercialization of Li-S batteries has been hindered by several challenges such as the insulating nature of sulfur, and the shuttling of soluble lithium polysulfides and accumulation of insulating deposits on the electrodes – leading to capacity degradation over extended cycling1.
Several research efforts have been devoted to mitigating these challenges. Among the different approaches, many studies focus on addressing the poor conductivity of sulfur and lithium polysulfide shuttling simultaneously by developing conductive carbon hosts2,3. While improvements have been achieved in the development of host structures with better electronic conductivity and improved polysulfide trapping capability, many of those structures have advanced architectures that demand complex processing, expensive precursors, and often lower gravimetric sulfur loading (<70 wt%).This leads to expensive-to-produce electrodes that have lower true energy density than desired. What is needed are simple preparation methods that address the issues discussed above without overly complicated processing, and preferably already commercialized materials.
In this work, we systematically investigate the effect of different electrode components, including various common carbons and polymeric binders. The effect of carbon type and loading is discussed. The effect of solvent to binder ratio in the electrode slurry preparation is also studied. By tuning the binder composition, types of conductive carbon black, and the amount of solvent, we observed a difference in the structure of the host medium and consequently the sulfur electrode. Specifically, a shell covering surrounding the sulfur particles was observed at low solvent/binder ratio. Increasing the solvent/binder ratio led to the disappearance of the shell coverings and particle agglomeration, which resulted in lower achieved capacity and reduced cycle life. Ketjen black offered the highest specific capacity, while the presence of shell covering achieved at a low solvent/binder ratio was found necessary for cycling stability.
This work demonstrates the importance of electrode processing parameters on the structure and electrochemical performance of sulfur cathode in Li-S batteries. The new understandings from this work can provide guidance on electrode designs to achieve Li-S batteries with enhanced capacity and longevity.
References

G. Li et al., Adv. Mater., 30, 1705590 (2018).

D.-W. Wang et al., J. Mater. Chem. A, 1, 9382 (2013).

Y. Li and S. Guo, Matter, 4, 1142–1188 (2021).
Tuning Exsolution of Nanoparticles in Defect Engineered Ruddlesden–Popper oxides for efficient CO2 electrolysis
Authors: Liu Zhengrong , Sun Yueyue , Yang Jiaming , Fu Lei , Zhou Jun , Wu Kai 
Published: September 2023

Solid oxide cell (SOC) is the energy conversion device with a series of advantages such as high efficiency, environmental friendliness and durability, making it a promising way to deal with environmental pollution and energy crisis appearing with the development of human society. Perovskite oxides with hetero-phases which were prepared by in-situ exsolution are widely used as fuel electrode in SOC. In this work, Ni-doped perovskites Ruddlesden–Popper oxides, (La, Sr)nTinO3n-2 with n = 5, 8, and 12 (LSTNn), were synthesized to design novel exsolution materials as solid oxide fuel cell anodes and for electrochemical catalysis applications.
Compared with pure LSTNn without Ni, a small A-site deficiency (10%) promoted the exsolution of Ni from the perovskite oxides of Ni-doped LSTNn. It is found that the morphology as well as electrochemical activity of LSTNn anodes can be successfully manipulated by the exsolution of Ni. Since more Ni nanoparticles are exsolved from the parent oxides, LSTN8 displays better electrochemical performance by providing more active sides during the hydrogen oxidation reaction and significantly lowering electrode polarization resistance. DRT analysis is conducted to study substeps of the whole electrode reaction, finding that in-situ precipitation improves rate-limiting steps much. The CO2 reduction reaction performance of LSTN materials is also studied, finding that in-situ grown nanoparticles on surface of LSTN significantly increases the density of surface active sites and three phase boundaries (TPBs), which are beneficial for CO2 adsorption and subsequent conversion.
It is clear from these results that varying Ni-doping in Ruddlesden–Popper oxides is a key factor in controlling the electrochemical performance and catalytic activity for hydrogen oxidation reaction in solid oxide fuel cells.
Efficient Ni-N-C Gas Diffusion Electrodes for Near Neutral and Acidic CO2 Reduction in a Zero-Gap Configuration
Authors: Brückner Sven , Ju Wen , Strasser Peter 
Published: September 2023

The electrochemical CO2 reduction can be a key technology for a fossil free future but for industrial applications it is necessary to analyse and understand the cathode. As one of the main problems is the low utilization efficiency of CO2 in AEM approaches due to the carbonate formation we have to find solutions to solve carbonate formation by maintain high selectivity.
In this work we investigated NiNC cathode GDEs for CO2 reduction to CO in a zero-gap MEA cell regarding their activity in a classic AEM, BPM and CEM approach. We show that the CO2 access of the catalyst is important to achieve a high performance. In an AEM approach with near neutral conditions on the anode we can reach 85% FE towards CO at 300 mA cm-2 at 3.6 V with single pass conversion of 40% which is close to the theoretical maximum. In addition, we can report high energy efficiency but only a utilization efficiency of around 50%.
Our newly introduced CCC value give information about the consumption of CO2 by the produced OH- during the CO2RR. The CCC value in combination with the selectivity enable insights in the mass transfer during the CO2 reduction in an AEM setup and give information about the accessibility of the catalyst and in addition we can monitor the flooding.
On the other Hand, we show that our NiNC GDE is stable under acidic conditions in a PEM and BPM zero-gap cell. The protons help to increase the utilization efficiency as the carbonate will react back to CO2 and water. Therefore, we investigated the activity with DI water and diluted H2SO4 at the anode and the protons in the BPM approach will be generated in situ due to water dissociation. In pure water, 0.01 and 0.1M H2SO4 we can achieve a selectivity above 80% towards CO at 100 mA cm-2 with cell potentials around 3 V which are comparable to the AEM configuration with 0.1M KHCO3. If we use a BPM approach, we can even push the single pass conversion towards CO to 70% at 500 mA cm-2.
The CCC value is in the perfect case 0 as we do not consume any additional CO2 but can indicating flooding as the CCC is rising. This indicates water accumulation which can hinder the neutralization of the carbonate/OH- and CO2 will be consumed and can precipitate in the flow channel.

Figure 1
Understanding the Role of Cu Electocatalyst, Binder, and Membrane Interfaces in CO2 Electrolyzer Durability
Authors: Hendershot John C , Bello Mustapha , Dauda Monsuru Olatunji , Flake John C. 
Published: September 2023

Carbon dioxide electrolyzers capable of maintaining stable performance for thousands of hours are necessary for commercial electrochemical reduction of CO2 to two-carbon products such as ethanol and ethylene. Currently, most studies containing CO2 reduction to two-carbon products have been for durations of under 20h. Only a few (<5) instances of CO2 reduction to two-carbon products at durations over 100h have been reported. Common cell failure mechanisms, such as carbonate salt precipitation and cathode flooding, can be mitigated by tuning the operating conditions of the reactor. Beyond these modes of failure, there are practical limitations related to materials' durabilities and long-term stabilities, including ionomeric membranes' operating lifetimes, gas diffusion cathodes, anodes, and other MEA components.
In this presentation, we explore the role of CO2, water, and ion transport on cell performance over extended periods of operation. The polymeric anion exchange membrane and conductive binder have been identified as crucial components in tuning the transport properties of electrolyzer systems and, thus, will be the focus of this study. We consider several types of anion exchange membranes (e.g., imidazolium, ammonium, piperindinium) and conductive binders (e.g., Nafion, PVDF, PTFE, PSMIM) for use in the direct reduction of CO2 to two-carbon products at nanoscale Cu electrodes (150mA/cm2, 0.01M KHCO3 anolyte). This work improves upon previous analysis of membrane and binder transport properties by testing a wider variety of materials for >100h durations and reporting specific cell failure times and causes. We will discuss the balances between carbonate precipitation, flooding, and other membrane or electrode failures as a function of materials, MEA preparation, and operating conditions. A comprehensive set of failure standards based on electrolyzer performance (pressure, outlet mass flow, two-carbon product Faradaic efficiencies, energy efficiency, carbon efficiency) is introduced, and electrolyzer configurations are tested in triplicate to produce statistically significant failure data. Overall, this provides insight into CO2, ion, and water transport's role in electrolyzer cell performance and failure mechanisms.

Figure 1
Performance Limitations in Ni-Rich, High-Energy Lithium-Ion-Battery Cathodes
Authors: Lindner Adrian , Both Svenja , Abdolhosseini Saeed , Menesklou Wolfgang , Danner Timo , Latz Arnulf , Krewer Ulrike 
Published: September 2023

Lithium-ion batteries with Ni-rich stoichiometries such as LiNi0.8Mn0.1Co0.1O2 (NMC811) have gained
importance due to the reduction of critical resources such as cobalt. While these cathode materials
with high nickel content offer high specific capacity [1], their rate capability is significantly reduced
compared to other chemistries. In the present work, the combination of large-volume FIB/SEM
tomography, structurally-resolved simulation, and electrochemical half-cell analysis is used to
characterize the cathode microstructure of a commercial high-energy cell. Detailed structural data
were obtained by FIB/SEM tomography and used to optimize the simulation approach to accurately
describe the discharge capacity and electrode impedance simultaneously. Poor electrical conductivity
is identified as the main cause of power loss. An optimized, artificial structure with up to 10% higher
1C discharge capacity compared to the original structure is developed by increasing and homogenizing
the conductive binder network. This tool enables further understanding of structural aging and
degradation effects by correlating structural changes with performance losses.
Acknowledgements
This work was funded by the German Ministry for Education and Research under the reference number
03XP0317D.
References
[1] A. Butt, G. Ali, K. Tul Kubra, R. Sharif, A. Salman, M. Bashir and S. Jamil, Energy Tech, 10(3),
2100775 (2022).
Figure 1: Virtual representations of a commercial cathode based on FIB/SEM tomography data. Three-dimensional analysis
allows for evaluation of volumetric phase contents, pore network diffusion and grain size distribution. Additionally, 3D data
acts as simulation domain for structurally resolved continuum simulations.

Figure 1
Development of Electrolyte Additives to Enable High-Voltage LiNi0.5Mn1.5O4 Lithium Ion Batteries
Authors: Cavers Heather , Wang Yajie , Kwade Arno 
Published: September 2023

Electrochemical energy storage (EES) is still key to realize wide spread use of renewable energies. For large-scale EES production, the development of high energy density, non-toxic, cost-effective materials is necessary. In this study, a cobalt free active material, Lithium Nickel Manganese Oxide, LiNi0.5Mn1.5O4 (LNMO), was employed in the production of cathodes for high voltage lithium ion battery (LIB) applications. LNMO is an attractive cathode active material due to its high operating potential (~4.7 vs. Li/Li+ [1]), non-toxicity and low cost. The practical application of LNMO cathodes in LIBs has been relatively limited, especially for large scale application, due challenges associated with the material (i.e. electrolyte decomposition at high voltage, self-discharge and dissolution of the transition metals [2]).
Electrolyte additives are an effective way to address these challenges, without major cost increase or changes to the production approach. In this study the role of different electrolyte additives in high-voltage full-cell LIBs with both graphite and silicon-graphite anodes is investigated. Additives known for their solid electrolyte interphase (SEI) forming ability (i.e. vinylene carbonate (VC) and fluoroethylene carbonate (FEC)), as well as additives that play additional roles such as cathode electrolyte interface formation or HF scavenging (i.e. tris(trimethylsilyl) phosphite (TMSP) and succinate anhydride (SA)), are used [3]. Galvanostatic cycling measurements were performed in 3-electrode cells in order to investigate the rate capability and long term cycling stability of LMNO/Gr and LMNO/Gr-Si full-cells with different electrolyte additives. The electrochemical characterization was verified with post mortem analysis to confirm the SEI composition, chemical and mechanical stability of the electrodes and lack of lithium plating. Post mortem investigations were done with Raman spectroscopy, scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) and optical microscopy. Improved rate performance and better long term cycling stability of both full-cell chemistries was achieved for electrolytes containing the TMSP additive.

References:

[1] G. Gabrielli, M. Marinaro, M. Mancini, P. Axmann and M. Wohlfahrt-Mehrens, J. Power Sources 351 (2017) 35-44.
[2] R. Amin, N. Muralidharan, R. K. Petla, H. Ben Yahia, S. A. Jassim Al-Hail, R. Essehli, C. Daniel, M. A. Khaleel, I. Belharouak, J. Power Sources, 467 (2020) 228318.
[3] K. Kim, H. Ma, S. Park, N.-S. Choi, ACS Energy Lett., 5 (2020) 1537-1553.
(Invited) Deciphering the Interplay between Thermodynamics and Kinetics during Cathode Calcination
Authors: Barai Pallab , Garcia Juan , Kinnibrugh Tiffany , Chen Ke , Wolfman Mark , Wang Xiaoping , Fister Tim , WANG Feng , Iddir Hakim , Srinivasan Venkat 
Published: September 2023

Synthesis of the cathode materials used in lithium ion batteries involve the two steps, coprecipitation and calcination, where in the first step cathode precursors are formed, and later in the second step lithium ions are inserted into these cathode particles through chemical routes. During calcination, the cathode precursors obtained from the coprecipitation is mixed with lithium salt (LiOH or Li2CO3) and heated at high temperatures (~ 650°C – 1000°C) where oxidation and lithiation of the cathode particles take place. Calcination is considered to be of major significance in determining the final state of the cathode particles because it not only determines the extent of oxidation and lithiation experienced by the cathodes, but also substantially influences its morphology (for example, primary particle size, internal porosity, etc.). Significant surface modification of the cathode particles is also possible during calcination, which can impact its charge transfer resistance. Before the oxidation and lithiation of the cathode precursors, removal of water or CO2 is observed. All these chemical changes within the cathode precursors lead to change in its lattice volume, which is reflected as variation in the size of the primary particles. Apart from this, sintering induced change in particle size is also observed during the calcination process.
In order to decipher the structural and morphological variations that occur during the calcination of cathode precursors, detailed experimental characterization is conducted in the present context using in situ X-ray diffraction (XRD) and thermogravimetric analysis (TGA) techniques. Atomistic simulations are conducted to decipher the feasibility of different chemical reactions that can possibly occur under elevated temperatures. Impact of reaction rate constant and mass transport in determining the extent of the oxidation and lithiation experienced by the cathode particles is analyzed by using a mesoscale level computational technique. Sintering induced grain growth experienced by the cathode primary particles is also investigated at the mesoscale level, which is demonstrated in Figure 1. Overall, a thorough understanding of the various physicochemical phenomena that occur during the calcination of cathode precursors has been developed using a combination of experimental and computational techniques, which will be discussed in detail.

Figure 1