bluuebunny/crossref_metadata_2025_split huggingface dataset:
Extending Cycle Life of Li-Ion Batteries Via Gas-Phase Nanocoating of Cathode Active Materials
Authors: Behboudikhiavi Sepideh , Moitzheim Sébastien 
Published: February 2024

The further penetration of the electric vehicles is dependent on the development of high-performance Li-ion batteries in terms of cost, cycle life, energy density, safety as well as sustainability. It is expected, in the short term, EVs will rely more on Li-ion technologies using active materials such as Ni-rich NMC cathode and Si anode for developing high specific energy and lower cost batteries1.
However, these active materials are facing multiple serious challenges which could hinder their targeted performance. Regarding this, Ni-rich NMC cathode active materials (CAM), in spite of their high energy density as a result of higher Ni content, tend to undergo dramatic capacity fade.
Since most degradation mechanisms are related to the surface of active materials, immense research and development efforts have been dedicated to surface modification techniques, and especially coating strategies2,3.
Examples of surface modification strategies include sol-gel, hydro/solvothermal deposition, and dry coating. A main drawback of these techniques is that they are not capable of precise control of the film thickness and uniformity. On the other hand, gas-phase coating techniques, such as atomic or molecular layer deposition, can address these shortcomings by offering a precise thickness control even in the range of angstroms and pinhole-free conformal coatings. As such, these coatings are better suited at mitigating interfacial degradation. Various nanocoating chemistries, such as oxides, fluorides, nitrides, phosphates and aluminates protect and stabilize the surface of Ni-rich cathode materials through the different pathways.
In this talk, we explore the benefits of gas-phase nanocoatings, and will show how we can produce surface modified Ni-rich CAM (e.g. NMC-811) in a continuous process that is ready for mass production.

References

M. S. E. Houache, C. H. Yim, Z. Karkar, and Y. Abu-Lebdeh, Batteries, 8 (2022).

D. Weber, Đ. Tripković, K. Kretschmer, M. Bianchini, and T. Brezesinski, Eur. J. Inorg. Chem., 2020, 3117–3130 (2020).

M. Lee et al., Chem. Mater., 34, 3539–3587 (2022).

Y. Zhao, K. Zheng, and X. Sun, Joule, 2, 2583–2604 (2018).
K0.5FeF3 as a New Zero-Strain Cathode Material for Lithium-Ion Batteries
Authors: Vogt Alexander , Geßwein Holger , Chable Johann , Baumann Aljoscha , Mutter Daniel , Urban Daniel F , Elsässer Christian , Lhoste Jérôme , Binder Joachim R. 
Published: February 2024

The stability of the cathode is of crucial importance for the service life of lithium-ion batteries (LIB). In the cathode, the lattice parameter usually changes during (de-)insertion of lithium, which causes various signs of aging that have a negative effect on the capacity of the cell. This problem can be tackled using a specific type of materials called zero-strain (ZS) materials. These materials do not show any (de-)intercalation-induced structural changes and stresses. Such a zero-strain effect was already demonstrated with fluorine-containing materials [1] and even for the similar material K0.6FeF3
[2] for sodium-ion batteries (SIB). In this case, potassium ions are removed in the first cycle and the vacant lattice sites can be used for the incorporation of sodium ions, while keeping the structural integrity of the host material.
Complementary to experiments, theoretical atomistic simulations are powerful to develop design criteria for further ZS-materials. Combining experiments and simulations in this work, the structural behavior of the material K0.5FeF3 was investigated when used as a cathode material in a LIB. The synthesis of K0.5FeF3 was achieved by a Rapid Microwave-Enhanced Solvothermal Process, which allowed to obtain the material in a TTB-type (Tetragonal Tungsten Bronze) phase with a high degree of purity. The material was then processed into electrodes, which were galvanostatically cycled against lithium metal. It was shown that the material is suitable for LIB as a cathode material. X-ray diffraction experiments showed that the lattice parameter changed by less than 1% after the incorporation of Li-Ions, in good agreement with the theoretical calculations conducted in parallel.

Lattice Parameter

Charged

Discharged

a[Å]

12.74±0.024

12.73±0.006

c[Å]

3.99±0.008

4.00±0.002

Volume [Å3]

647.57±2.67

647.75±0.76

This work was supported by the German Research Foundation (DFG) BI 1636/7-1 and EL 155/29-1.

References

[1] De Biasi, L., et al. Journal of Power Sources, 2017, 362. Jg., S. 192-201.
[2] Han, Y., et al. Journal of Materials Chemistry A, 2016, 4. Jg., Nr. 19, S. 7382-7389.
Figure 1: Diffractograms of an electrode with K0.5FeF3, which was measured before use and an electrode after the first successful discharge, down to a voltage of 1.8 V.

Figure 1
In-Situ Formation of Low-Strain and Defect-Free Single Crystal NMC in Electrode Slurries
Authors: Carrier Laurie , Obrovac Mark 
Published: February 2024

Synthesis of cathode materials for lithium-ion batteries usually results in agglomerations of single crystals.[1][2] Jet milling is commonly used in industry to deagglomerate cathode material powders.[3] However, dry grinding techniques can often lead to the introduction of defects, requiring a reheating step to reform pristine NMC. Wet milling in water has also been proposed, however, this results in lithium loss and crystal defects, again requiring additional drying and reheating steps are required to reform pristine NMC.[4][5]

Here we report a low-strain and defect-free NMC deagglomeration method that is performed in-situ during the electrode slurry dispersion process. In this method, cathode material, conductive additive and binder are planetary milled in N-methyl-2-pyrrolidone (NMP). This results in both the deagglomeration of cathode secondary particles and the formation of a well-dispersed electrode slurry. Figure 1(a-d) compares the SEM images of NMC samples deagglomerated by different dry grinding techniques and the in-situ slurry milling method. Figure 1(e) and (f) show lattice strains and the first cycle voltage curves of the same samples. In comparison to the dry grinding techniques, in-situ slurry milling was found to be more effective in secondary particle deagglomeration than dry methods and resulted in a single crystal NMC with the lowest lattice strain, lowest irreversible capacity, and highest coulombic efficiency. In fact, in-situ milling was found to reduce lattice strain compared to the original agglomerated cathode material, by relieving internal strains created at the grain boundaries of secondary particles. We believe that in-situ slurry milling is an effective method for NMC particle deagglomeration and improving NMC performance.

References:

[1] Zheng, L.; Bennett, J.C.; Obrovac, M.N. J. Electrochem. Soc.
2020, 167, 130536.
[2] Lee, S.-Y.; Park, G.-S.; Jung, C.; Ko, D.-S.; Park, S.-Y.; Goo Kim, H.; Hong, S.-H.; Zhu, Y.; Kim, M. Adv. Sci.
2019, 6, 1800843.
[3] Gommeren, H.J.C.; Heitzmann, D. A.; Molenaar, J. A. C.; Scarlett, B . Powder Technol.
2000, 18, 147-154.
[4] Kumakura, S.; Paulsen, J.; Yang, T.; Yang, H. Han, S.-Y. US 2020/0381727 A1, 2020.
[5] Paulsen, J.; Kumakura, S.; Yang, T.; Kim, D.-H.; Yang, H. US 2021/0143423 A1, 2021.

Figure 1
Dual Electrolyte Design for Lithium-Ion Batteries
Authors: Pechberty Clément , Reiner Sofia , Johansson Patrik 
Published: February 2024

Lithium-ion batteries (LIBs) are today the most used energy storage for portable electronics and electric vehicles – but are laden with concerns of materials scarcity and availability. The development of high-voltage cobalt-free cathode active materials such as LiNi0.5Mn1.5O4 (LNMO) represents one promising route for next-generation LIBs due to their combination of high capacity and low cost. Combining LNMO with conventional LIB electrolytes based on carbonate solvents, however, typically leads to severe capacity fading due to a range of different degradation mechanisms1, not the least due to the wide electrochemical stability window (ESW) needed for a graphite//LNMO cell.
Here we use the rather novel route to design LIB cells by utilizing two different electrolytes to together cover the full ESW2. The separation of the two electrolytes is assured by designing them to be immiscible, either chemically or more mechanically, while for the functionality of the cell we also monitor the evolution of a stable solid electrolyte interphase (SEI) at the anode side and a stable cathode electrolyte interphase (CEI) at the cathode side. This proof-of-concept study allows us to shine light on the best ways to design a dual electrolyte cell.
References

K.
Guo et al.
,
“
High‐Voltage Electrolyte Chemistry for Lithium Batteries
”,
Small Science 2, 2100107 (2022).

S.
He et al.
,
“
Design of a Dual-Electrolyte Battery System Based on a High-Energy NCM811-Si/C Full Battery Electrode-Compatible Electrolyte
”,
ACS Appl Mater Interfaces 13, 54069–54078 (2021).
Thin-Film SiOx Coated Carbon Nanofibers As Stable Anodes for Lithium-Ion Batteries
Authors: Kim Na-Yeong , Jung Ji-Won 
Published: February 2024

With the increase in the capacity of cathode materials in lithium-ion batteries(LIBs), the demand for novel anode materials with high theoretical energy density is following. Up to now, many candidates have been reported; silicon-based composites are considered a prospective alternative due to their abundant reserves and high energy density. However, The primary disadvantage of Si, electrochemical irreversibility during the charge/discharge process, hinder widespread use.
In this study, we adapted SiOx-coated carbon nanofibers (SiOx-CNFs) composite to the binder-free anode current collector for lithium-ion batteries. The composite has a structure where a thin amorphous SiOx (thickness ~100nm) is coated on the CNFs surface and is successfully synthesized by electrospinning and sputtering. This structure, surface SiOx-coated porous CNF, breaks through the significant drawback of Si-based composites, pulverization of Si element during the charge/discharge cycle. In addition to this, due to the structure of porous CNF, we achieved the curtail of electrode weight.
Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD) analyses are carried out to confirm the morphology and crystallinity. Furthermore, with cyclic voltammetry analysis, fast reaction kinetics and excellent electrochemical reversibility are verified. The cycle test is also conducted to prove excellent capacity and cyclic stability.
Life Cost Assessment of Using Binders of Sulfide-Based All Solid-State Lithium Batteries for Lithium-Ion Batteries
Authors: Montes Susan , Beutl Alexander , Jahn Marcus , Tron Artur 
Published: February 2024

PVDF is commonly a binder used for cathode materials in generation 3 Li ion batteries due to the good binding ability to active material and the current collector with reasonable electrochemical stability and maintaining facile lithium transport. However, organic solvent N-methyl pyrrolidone (NMP) is required for the preparation of slurry in order to dissolve PVDF [1]. These drawbacks of high cost and environmental issues are worsened by the fact that PVDF can easily react with components of liquid electrolytes with possible formation of LiF leading to the unstable performance [2]. Furthermore, fluorinated polymers are considered an environmental risk and are a major concern for recycling efforts [3]. Therefore, reducing the use of polyvinylidene difluoride binder in combination with toxic and expensive N-methyl pyrrolidone (NMP) organic solvent, resulting in safe use and utilization during the battery manufacturing process, is the aim of this work. Here, the sulfide solid state binders are attractive candidates for the anode and cathode composites from the point of view of environmentally friendly use of materials, low cost, and easy electrode processing with subsequent disposal. This study reports the performance of the cathode and anode materials applied to these types of binders and reference binders of polyvinylidene difluoride (PVDF) for these as-obtained samples for lithium-ion batteries. The obtained cathode and anode materials are analyzed by XRD and SEM methods. The electrochemical performance of the obtained electrodes is tested by galvanostatic cycling, cyclic voltammetry, and electrochemical impedance spectroscopy. The obtained electrodes exhibit stable electrochemical performance due to the better uniform distribution of electrode particles with strong adhesion to the current collector for long cycle life and stable formed SEI layer compared to the PVDF-based sample. In addition, these samples maintain stable cycle life after various rate capabilities due to the facilitated lithium-ion diffusion and electronic conductivity.

Acknowledgments

This work was supported by the financial support of the Austrian Federal Ministry for Climate Action, Environment, Energy, Mobility, Innovation and Technology.

References

[1] G.B. Xia, L. Cao, G.L. Bi, A review on battery thermal management in electric vehicle application, J. Power Sources 367 (2017) 90–105.
[2] D. Bresser, D. Buchholz, A. Moretti, A. Varzi, S. Passerini, Alternative binders for sustainable electrochemical energy storage – the transition to aqueous electrode processing and bio-derived polymers, Energy Environ. Sci. 11 (2018) 30963127.
[3] R. Lohmann, I.T. Cousins, J.C. DeWitt, J. Glüge, G. Goldenman, D. Herzke, A. B. Lindstrom, M. F. Miller, C. A. Ng, S. Patton, M. Scheringer, X. Trier, Z. Wang, Are Fluoropolymers Really of Low Concern for Human and Environmental Health and Separate from Other PFAS? Environ. Sci. Technol. 54 (20) (2020) 12820–12828.
Battery Production Solvent Alternative to NMP - Jeffsol® MEOX
Authors: White Victoria , Zhou Hui , Zhang Ke , Gazda Jerzy , Lacey Steven David 
Published: February 2024

Solvents are commonly used in in battery manufacturing to dissolve binders, aid in slurry dispersion, stability, and the coating process [1]. For the cathode, N-Methylpyrrolidone (NMP) is the commonly used solvent for working with PVDF binder. However, it has been classified as Reprotoxic, and labeled as a CMR substance. Due to the classification, there are existing strict emission regulations and increasing regulations on the handling and use of the solvent [1,2]. As a result of these regulations with NMP, there has been increased interest for replacements that can improve the safety without significantly affecting the existing processes. Huntsman has developed JEFFSOL® MEOX, a solvent which may be less hazardous to handle while having similar performance capability to NMP.
JEFFSOL® MEOX and NMP are both clear, colorless, and odorless aprotic solvents. They also share similar dipole moments and dispersion energy parameters. Therefore, JEFFSOL®MEOX may have an advantage in solubility performance in some applications when compared with other NMP alternatives (Table 1). Due to these comparable characteristics and the ease of handling, JEFFSOL® MEOX can be used in a wide variety of applications. In addition to use as a solvent for PVDF or PAN binders in batteries, JEFFSOL® MEOX can be applied in chemical reactions and polymerization applications [3]. Due to its usefulness in multiple markets, there are multiple grades of MEOX available, including E-Grade® MEOX which contains ultra-low metals and can be used in semiconductor production without contaminating the wafer.
As an example of the comparable solubility performance, Figure 1 shows results of NMP and JEFFSOL® MEOX with multiple PVDF samples that are commonly used in battery production, including mono- and co-polymers of low and high molecular weights. With both solvents, heat and agitation decreased the time needed to fully dissolve the PVDF.
In addition to MEOX, Huntsman offers other experimental solvents which could be used as NMP replacements as well. In addition to the range of solvents currently offered, Huntsman has the capability to synthesize new solvents based on user feedback. This Huntsman technology gives users greater flexibility and capabilities in selecting the ideal solvent for their unique processes while shifting away from NMP.
This presentation shows the latest results with JEFFSOL®MEOX benchmarked against industry standard NMP.
[1] Y. Liu, R. Zhang, J. Wang, Y. Wang: Current and future lithium-ion battery
manufacturing (iScience, Volume 24, Issue 4, 2021)
[2] REACH COMMISSION REGULATION (EU) 2018/588 (2018)
[3] V. White. H. Zhou, K. Zhang, J. Gazda: Advanced Battery Materials as reported at the International Battery Seminar (2023)

Figure 1
On the Chemo-Mechanics of Advanced Electrode Materials Via Operando Acoustic Transmission
Authors: Sun Kerry , Thorsteinsson Gunnar , Zhao Dingyi , Steingart Daniel A. 
Published: February 2024

Silicon anodes have emerged as a viable strategy for a negative material in solid-state batteries to balance their reactivity with high energy density. Compared to conventional graphite electrodes, silicon anodes have a large theoretical capacity of 3600 mAh/g compared to 372 mAh/g in graphite. This large capacity comes from the fact that lithiated silicon (Si4Li15) can accommodate 15 Li atoms per 4 Si atoms as opposed to LiC6. As a result, silicon anodes experience large volumetric expansions up to ~300% as Li ions alloy into the Si negative electrode. Acoustic transmission utilizes sound propagation to nondestructively probe electrode chemo-mechanics in operando.
c = √(E/ρ)
The speed of sound through a material is proportional to its Young’s modulus (E) and inversely proportional to density. Previous works have shown that acoustic transmission can detect gas formation and dewetting in commercial Li-ion cells and Li metal cells. There has also been a study showing acoustics can detect void formation during Li stripping in solid-state Li symmetric cells. To the best of our knowledge, there has not been an acoustic study of an all solid state Li full cell.
This work intends to show that acoustic transmission can monitor Si expansion and contraction as a function of waveform damping and the Young’s modulus of the Si electrode. This works gives insight into the mechanical considerations and possible loss of contact as Si lithiates and delithiates repeatedly. The reliance of Si anodes on stack pressure is not well understood and is further elucidated in this work. We hope to give a better understanding of the intersection between the electrochemical reactions at the Si electrode and the mechanical stresses induced on the cell.

Figure 1
Technoeconomic Assessment of Large-Scale Ethylene Production via the Electrochemical Reduction of CO2
Authors: Flake John , Bachar Cameron , Dalum Albert S , Huynh Bruce , Porta Hannah , Ramaraju Rahul , Sheets Ella , Yi Hingyu , Guillory Barry , Pendergast John , Jiao Feng 
Published: February 2024

In the last five years, several works have shown that CO2 may be electrochemically reduced to C2 products such as ethylene at current densities over 1 A cm-2 and Faradaic efficiencies over 70%. For the first time, these current densities and Faradaic efficiencies are comparable with commercial electrolytic processes. For reference, over 100 million metric tons per year of chlorine per is manufactured via the Chlor-alkali process at current densities near 0..4 A cm-2 and Faradaic efficiencies to Cl2 over 80%. While the current densities and Faradaic efficiencies for CO2 reduction are compelling; other metrics such as energy efficiency, selectivity, carbon efficiency, electrolyzer scaling, electrolyzer costs and post-electrolysis separation are not yet at the levels needed for commercialization.
In this presentation, we consider the technoeconomics of ethylene production at large scales (25,000 to 150,000 metric tons per year). We investigate the impact of cell potential, Faradaic efficiencies, conversion level, process scaling and post-electrolysis separations on the cost of electrolytic ethylene production. Our results indicate that the “green” ethylene made using CO2 as a feedstock requires anywhere from approximately 1 to 10 times greater manufacturing costs than conventional cracking of ethane depending on factors such as electrical energy cost, electrolyzer costs and other parameters. In this case, we consider key technical and economic needs including: price premiums, tax incentives, CO2 emission taxes, and other factors that could enable electrolytic ethylene manufacturing at large scales within the next decade.
Durability of CO and CO2 Electrolyzers with Copper Electrocatalysts, Gas Diffusion Electrodes, and Anion Exchange Membranes
Authors: Flake John C. , Bello Mustapha , Dauda Monsuru Olatunji , Hendershot John C , Gonçlaves Ricardo , Jiao Feng , Yan Yushan , Yao Koffi 
Published: February 2024

Recent works have shown that the electrochemical reduction of CO2 or CO to C2 products may be carried out at high rates and selectivities using electrolyzers with copper catalysts, gas diffusion electrodes (GDEs), and anion exchange membranes (AEMs). The current densities and Faradaic efficiencies reported for CO2 reduction are similar to those used in the commercial production of chlorine via the Chlor-alkali process; however, other performance metrics related to the energetic efficiency, carbon efficiency, single-pass conversion, crossover, and durability or operating lifetime are also important considerations.
Work in our labs indicates that operating lifetimes are typically related to flooding, precipitation, or catalyst deactivation. As shown in Figure 1a, flooding in CO2 electrolyzers is typically observed with a sharp increase in hydrogen production and increased cathode gas flows. Figure 1b shows evidence of carbonate precipitation including variations in cell potential and lower cathode flow.
In this talk, we consider the relationships between AEM properties (conductivity, water transport, counter ion transport), binder properties (viz. hydrophobicity), and catalysts on operating lifetimes of CO2 electrolyzers.

Figure 1