bluuebunny/crossref_metadata_2025_split huggingface dataset:
Improvement of Ionic Conductivity in Li7La3Zr2O12 (LLZO) Solid Electrolyte By Doping with Aluminum/Tungsten
Authors: Hong Da-been , Park Jae-wan , Shim Jae-Hyun , Kim Moon-Sung 
Published: February 2024

Recently, there has been increasing interest in solid electrolytes, which are the most important materials in all-solid-state lithium-ion batteries. Among all solid electrolytes, garnet-type Li7La3Zr2O12 (LLZO) has been proven to be one of the most promising electrolytes due to its high Li+ conductivity, wide potential window, and electrochemical stability towards metallic lithium anode. In particular, cubic garnet-type LLZO solid electrolytes have received a lot of attention for the development of high-performance all-solid-state batteries with safety, energy density, and long cycle life. In this study, we synthesized LLZO solid electrolyte powders with garnet structure and determined the optimal composition and sintering temperature by adding Al/W to form a stable cubic phase.
In this study, Al or W-doped LLZO were prepared by a post-doping method. In this process, LLZO powder was first prepared, and then mixed with Al2O3 or WO3 powders to produce doped LLZO ceramic electrolytes, respectively. During this process, the doped ions entered the LLZO lattice, increasing the lithium ion transport channels and promoting lithium ion conductivity. The sintering time, crucible, and sintering temperature were adjusted to investigate the optimal process conditions of the post-doping method. As a result, the doped solid electrolyte exhibited high lithium ion conductivity and low activation energy. Using the high lithium ion conductivity and broad electrochemical stability window of the Al or W doped LLZO SSE, the (NCM622)/(Al or W doped-LLZO) cell delivered a steady cycle for 100 cycles at 0.1C. The Al or W doped-LLZO prepared in this study showed advantages of high conductivity, simple preparation process, high reproducibility, and low cost, which provides technical support and reference for further application of garnet-type SSEs in solid-state batteries with high energy density.
Towards Sustainable Lithium-Ion Battery Anodes: Addressing the Critical Need for Graphite Recycling
Authors: Oftedal (Naldoni) Liv (Clicia) , Skomedal Gunstein , Hansson Robin 
Published: February 2024

Graphite is the predominant anode material for all lithium-ion batteries (LIB) currently manufactured. However, despite comprising between 10 and 20 percent of a LIB's weight, graphite is not typically recycled. Graphite has a wide variety of applications outside of LIB, but the value of use in other applications is very low, so only recycling graphite back into anode material will be economically viable. Since graphite is such a stable substance, it should in theory be highly desirable for direct recycling back into anode material. As a result of this stability, several sources of graphite can become intermixed and impossible to separate later, posing a traceability issue. As is the case with cathode materials, there is currently no policy mandating the recycling of graphite.
At the same time, graphite (natural) is on the EU's list of critical raw materials (98% imports), and the global supply of graphite for anode materials is entirely dominated by China. The production of natural and synthetic graphite has significant environmental costs, with recent studies indicating a CO2 footprint in the range of 10 to 30 kgCO2/kg graphite, which is significantly higher than what was previously reported in LCA literature. There is a need to establish processes for recycling this valuable material, as its demand is expected to increase dramatically over the next decade.
In recent years, Vianode has developed a one-of-a-kind method for converting graphite concentrates from LIB production scrap and end-of-life batteries (black mass) back into anode-grade graphite for use in new LIB. Using a high temperature purification stage, impurities and flaws in graphite can be effectively removed and a purity of over 99.99% can be attained. Cell testing reveals that recycled graphite can achieve the same properties as virgin graphite, including outstanding reversible capacity, first cycle efficiency, fast charge capability, and cycle life. The results indicate that graphite recycling should be implemented as soon as possible to lessen the EU's reliance on graphite imports and significantly reduce the environmental impact of anode materials in LIB.
Experimental Analysis of the Current Distribution between Graphite and SiOx in Blend Electrodes for Lithium-Ion Cells
Authors: Knorr Julian , Kufner Thomas , Adam Alexander , Danzer Michael Anton 
Published: February 2024

The demand for battery cells with increased energy density without sacrificing performance is driving research into investigating new active electrode materials. The addition of silicon oxide as a second active anode material alongside graphite, referred to as graphite/SiOx blend electrodes, offers a great opportunity to increase the specific capacity of lithium-ion cells. The stable structure of graphite in combination with the high theoretical capacity of silicon represents a promising improvement, for example to increase the driving range of electric vehicles.
In this work, the electrochemical behavior during the lithiation and delithiation process of blend electrodes is analyzed. Two custom-made cells are connected in parallel, with each of the cells containing either pure graphite or pure SiOx as the working electrode. Both cells use similar counter electrodes. The experimental setup enables the measurement of the current distribution during charging or discharging of the parallel connection. The observed individual current flow to each cell represents the current flow to each active material. This allows conclusions to be drawn about of the electrochemical processes in a graphite/SiOx blend electrode [1].
This work focuses on two effects of blend electrodes: First, the lithiation differences between the active materials with increasing charge rates. Changes in the lithiation distribution between the active materials are observed at higher currents. Second, the effect of hysteresis on the lithiation of blend electrodes. When stating the lithiation process with a fully or partially delithiated blend electrode, the increased delithiation potential of SiOx [2] causes differences in the lithiation distribution between the materials. The knowledge gained on graphite/SiOx blend electrodes contributes to a better understanding of lithium-ion cells and to the optimization of their integration in electric vehicles.
References
[1] Heubner, Christian, et al. "Understanding Component‐Specific Contributions and Internal Dynamics in Silicon/Graphite Blended Electrodes for High‐Energy Lithium‐Ion Batteries." Batteries & Supercaps 5.1 (2022): e202100182.
[2] Jiang, Yang, et al. "Voltage hysteresis model for silicon electrodes for lithium ion batteries, including multi-step phase transformations, crystallization and amorphization." Journal of The Electrochemical Society 167.13 (2020): 130533.
Lithium-Ion Battery Electrolyte Miscibility Studied By Spectroscopy
Authors: Reiner Sofia , Pechberty Clément , Maibach Julia , Johansson Patrik 
Published: February 2024

Interfaces, interphases, and surfaces are of immense interest to the battery research community since the key reactions and much of the kinetics that determine the performance of the cell occur there. While solid/liquid and solid/solid interfaces have been thoroughly studied, liquid/liquid interfaces have attracted much less attention.
Here we target the liquid/liquid interfaces between two liquid electrolytes, employed to create dual electrolyte batteries. The grand idea is that based on two either chemically or mechanically immiscible electrolytes we can expand the overall electrochemical stability window to achieve both high electrolyte oxidation stability on the positive electrode and efficient and stable solid electrolyte interphase (SEI) formation on the negative electrode [1][2].
To understand the dual electrolyte systems created we study diffusion across the liquid/liquid interfaces, the formation of any emulsion layers, and if there are chemical reactions occurring. We use confocal Raman spectroscopy focusing on the interface between two porous separators soaked with two different electrolytes as well as in situ Raman depth profiling with micrometer resolution, including the role of pressure to the stack of separators (both glass fibre and polymer based).
The observations of for example diffusion and mixing are subsequently correlated with the physicochemical properties of the two electrolytes in order to pave the way for rational design of a dual electrolyte cell.
[1] S. He, S. Huang, Y. Zhao, H. Qin, Y. Shan and X. Hou. “Design of a Dual-Electrolyte Battery System Based on a High-Energy NCM811-Si/C Full Battery Electrode-Compatible Electrolyte”. ACS Applied Materials & Interfaces 2021 13 (45), 54069-54078. DOI: 10.1021/acsami.1c17841
[2] Ren, Y., Manthiram, A., “A Dual-Phase Electrolyte for High-Energy Lithium–Sulfur Batteries. Adv. Energy Mater”. 2022, 12, 2202566. https://doi.org/10.1002/aenm.202202566
Why Li(1-x)FePO4/ LiFePO4 Is a Good Candidate to be Used as Reference Electrode
Authors: Genies Sylvie , Balfet Pierre , Villemin Elise , Septet Cédric , Ranieri Marco , Franchi Romain , Raccurt Olivier 
Published: February 2024

Fundamental electrochemical studies require the implementation of a reference electrode inside the cell to record the potential profile and characterize the kinetic properties as well as the interface structure of each electrode [1]. Obtaining such data is essential for a better understanding of the electrochemical processes and the aging mechanisms generated by cycling. This is challenging for lithium-ion technologies for which no reference electrode is commercially available. LixFePO4 (LFP), a biphasic material, has been identified as a possible reference material, because its insertion/de-insertion curves show a voltage plateau over a wide lithiation range (Figure 1). Literature reports studies of instrumented pouch cells with a reference electrode in LFP [2, 3]. One important criterion to consider is the stability of the potential of LFP over time and the impact of temperature on the potential in the perspective to develop innovative smart-cell. The response will be provided according to the stability study of the Li0.5FePO4 potential. The methodology, used to evaluate the operating time of the reference electrode in LFP is based on monitoring the open circuit potential (OCV) of Li0.5FePO4 versus lithium over time and at different temperatures. The used cell configuration used is illustrated in Figure 2. We will also present the entropic behaviour of LFP which will confirm why LFP is a good candidate for reference electrode.
REFERENCES:
[1] Electroanalytical Methods Guide to Experiments and Applications, Springer; Edition: 2nd ed. 2010 (11 November 2014)
[2] I. Jiménez Gordon, S. Grugeon, A. Débart, G. Pascaly, S. Laruelle, Solid State Ionics 237 (2013) 50–55
[3] F. La Mantia, C.D. Wessells, H.D. Deshazer, Yi Cui, Electrochemistry Communications, Vol. 31,2013, 141-144
ACKNOWLEDGMENTS:
INSTABAT project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 955930.

Figure 1
Analysis of Structural Changes in Practical Batteries during Overcharging Using Synchrotron X-Ray CT Imaging
Authors: SHI Xian , Watanabe Toshiki , Yamamoto Kentaro , Kato Shiro , Fujii Masanori , Kinoshita Hajime , Matsunaga Toshiyuki , Uchimoto Yoshiharu 
Published: February 2024

Lithium-ion rechargeable batteries are desired for applications such as power sources for electric vehicles, which require increased energy density to extend cruising range. In the cathode, increasing the nickel content makes it possible to increase the energy density, but this is problematic due to a decrease in safety. To solve this problem, it is necessary to clarify the phenomena leading to structural breakdown by operando observation[1]. We have developed a system for operando non-destructive observation of the internal structure of all batteries under transient conditions using 100 keV collimated light of SPring-8 beamline. In this study, the difference in the behavior of LiCoO2 (LCO), LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNi0.8Mn0.1Co0.1O2 (NMC811) during overcharging was discussed in combination with the measurement of the electronic structure of the cathode active materials from the surface to the bulk.
A 40-layer laminated battery (1 Ah) was used, with LCO, NMC622 and NMC811 as the cathodes and natural graphite as the anode. After charging to 100% SOC at 1C (1C=160 mAh/g) rate at room temperature, the overcharge process performed under 3C and/or 6C rate from 100% SOC while measuring voltage and temperature. Overcharge behavior inside the battery was observed simultaneously by operando X-ray CT during overcharge process.
During the overcharge test at 6C rate, the maximum temperature of the LCO laminated battery was 390 ℃, while NMC811 laminated battery reached over 600 ℃ (Fig. 1). Point 1 in Fig. 1 is the point where changes in the electrode structure begin to be observed by the operando X-ray CT measurements. The point 1 of NMC811 occurred earlier (203 s) than LCO (542 s). From the O-K XAS result (Fig. 1d), the pre-edge (located at 519 ev) of NMC811 was much higher than LCO and NMC622 when overcharging to 200% SOC, meanwhile the O-Ni bond in NMC is more unstable than O in LCO in the overcharged state. The unstable electronic structure of oxygen on the surface of NMC811 is the starting point for the rapid structural change of the battery during overcharging.

Reference
s
:

[1] Donal P. Finegan; Mario Scheel; James. Robinson; Bernhard T.; Marco Di M.; Gareth H. Phys.Chem.Chem.Phys. (2016), 18, 30912.

Figure 1
Transition Metal-Doped Co-Free Layered Cathode for High-Performance Li-Ion Batteries
Authors: Park Geontae , Kim Myoung-Chan , Sun Yang-Kook 
Published: February 2024

Surging demand for high-energy-density cathodes based on Li(Ni
x
Co
y
Mn1−x−y
)O2 (NCM) and Li(Ni
x
Co
y
Al1−x−y
)O2 (NCA) for LIBs for EVs has tripled the price of Co in three years. As the price of Co rises rapidly, efforts to remove Co from the cathodes are increasing, but Co, even in minute amounts, plays an essential role in maintaining rate capability and structural stability while reducing cation mixing.1 So the realization of high-performance, Co-free layered cathodes poses a serious technical challenge. Recently, LiNi0.9Mn0.1O2 (NM90) was proposed as an alternative Ni-rich, Co-free cathode material.2 Although the long-term cycling stability of the NM90 is acceptable, its capacity is substantially less than that of a LiNi0.9Co0.05Mn0.05O2 (NCM90) when the NM90 is charged to a standard operating voltage (4.3 V) because the charging ends in the midst of the second hexagonal phase (H2) to the third hexagonal phase (H3) transition. In this study, we investigate to stabilizing the delithiated structure of an NM90 cathode at 4.4 V is proposed, namely, the introduction of a tertiary element into the cathode in combination with the modification of the electrolyte. The introduction of 1mol% Mo into NM90 accompanies increasing in the upper cut-off voltage to 4.4 V (versus Li+/Li) can help realize a half cell, delivering a capacity of 234 mAh g-1 that is comparable to that of NCM with similar Ni contents. The cycling stability of a full cell featuring the Li(Ni0.89Mn0.1Mo0.01)O2 (Mo–NM90) cathode is enhanced with a modified electrolyte (EF91, EMC:FEC = 9:1); retaining 86% of its initial capacity after 1,000 cycles while providing 880 Wh kgcathode
−1. Mo–NM90 cathode is able to deliver a high capacity with cycling stability suitable for the long service life for electric vehicles at a reduced material cost, furthering the realization of a commercially viable Co-free cathode for LIBs.

Reference
s
:

[1] C. Delmas, I. Saadoune, A. Rougier, J. Power Sources, 44 (1993) 595-602.
[2] A. Aishova, G.-T. Park, C. S. Yoon, Y.-K. Sun, Adv. Energy Mater. 10 (2019) 1903179.
Development of a Polymer-Based Silicon-NMC Solid-State Cell
Authors: Giffin Guinevere A. , Goettlinger Mara , Bohn Hendrik , Peters Simone , Weller Mario , Naßmacher Alexander , Brändel Timo , Friesen Alex 
Published: February 2024

Solid-state batteries are seen as the next generation of battery technology with the promise of high energy density and improved safety as compared to conventional lithium-ion batteries. To achieve these goals, high-capacity negative electrodes, e.g., silicon or lithium, need to be combined with high capacity and high voltage positive electrodes, e.g., Ni-rich NMC. This combination of active materials provides a number of significant challenges for the solid-state electrolyte. If silicon is used as the anode active material, significant volume changes during lithiation/delithiation occur. These volume changes lead to a variety of problems including irreversible loss of lithium and eventual disintegration of the electrodes, resulting in capacity fade. Therefore, the electrolyte must be sufficiently elastic to buffer these changes. If Ni-rich NMC is used as a cathode active material, then the electrolyte must be stable at voltages up to at least 4.2 V. There are currently few, if any, electrolyte solutions that can address these challenges simultaneously.
In the ASTRABAT project, a silicon-NMC solid-state cell has been developed based on two tailored polymer electrolytes, which allows the specific challenges of each cell compartment to be addressed separately. A vinylidene fluoride copolymer-based electrolyte has been developed for use as a catholyte and a hybrid inorganic-organic polymer electrolyte as the anolyte. This work will report a characterization of both electrolytes, along with their electrochemical performance in solid-state half-cells and full-cells.
Synthesis and Characterization of Vitrimer-like Self-Healing Polymer Electrolytes for Lithium Metal Batteries
Authors: Barakat Carla , Jia He , Gohy Jean-François 
Published: February 2024

Solid-polymer electrolytes have become crucially significant with the fast-expanding energy requirements in both the academic and industrial spheres due to their better safety and energy density compared to liquid electrolytes. Despite these encouraging possibilities, a few obstacles are associated with these electrolytes, chief among them being the limited charge transport via the solid electrode-electrolyte interface. Due to the difference in electrochemical potential between the electrode and the electrolyte, this obstruction initiates electrode-electrolyte interactions through electrode volumetric changes, interface reactions, and space charge layers.
One possible way to enhance the LIB performance could be by integrating a new class of covalent adaptable networks called vitrimers.
The self-healing, shape memory, recyclability, and reprocessibility properties of vitrimers, a class of covalent adaptable networks (CANs), are derived from a covalent molecular network that can change its topology through molecular rearrangements while maintaining the overall number of network bonds. In this manner, Li dendrites that might develop during battery cycling could be eliminated and the electrolyte-electrode contact could be restored by vitrimers.

Figure 1
Si-Drive European Project: Developing Crosslinked Polymer and Composite Membrane Electrolytes for Lithium-Based Batteries
Authors: Falco Marisa , Gerbaldi Claudio , Saffirio Sofia , Smeacetto Federico 
Published: February 2024

Currently the main application of lithium ion batteries is in portable electronics, but new emerging applications such as electric cars require lower cost, improved cycle life, sustainability, safety and energy density.
The ambition of Si-DRIVE European project is proposing next-generation batteries for electric cars built in Europe, designed to ensure recycling above 50%. Si-Drive battery will contain a Silicon anode, which has a high specific capacity, and a high voltage cathode without cobalt to reduce the cost and improve sustainability.
As an alternative to conventional organic solvents, ionic liquids have been widely investigated over the years, due to their excellent properties in terms of safety and stability.
The 1st generation of electrolytes for Si-Drive includes selected ionic liquids with high ionic conductivity and wide electrochemical stability. The 2nd generation of electrolytes combines the ionic liquids and the precursors of the polymer matrix in the formulation, in order to obtain crosslinked self-standing flexible films. The addition of ceramic super lithium ion conductors to obtain composite polymer electrolytes is also envisaged to improve the electrochemical stability window of the electrolyte.
Here we present several different polymer electrolytes and semi interpenetrating polymer networks encompassing ionic liquids and ceramic materials having ionic conductivity > 10 mS/cm at 20 °C, which can be in situ-deposited and crosslinked on top of the electrodes, and combined to form bi-layered electrolyte membranes to tune the compatibility with the electrode materials. The cycling performance with different positive and negative electrodes at ambient temperature is also demonstrated.

Acknowledgements:

The Si-DRIVE project has received funding from the European Union’s Horizon 2020 Research&Innovation programme, under Grant Agreement 814464.

References

J.-Y. Hwang, S.-T. Myung, Y.-K. Sun, Chem. Soc. Rev. 46, 3529-3614 (2017)

M. Falco, C. Simari, C. Ferrara, J.R. Nair, G. Meligrana, F. Bella, I. Nicotera, P. Mustarelli, M. Winter, C. Gerbaldi, Langmuir 35, 8210-8219 (2019)

M. Falco, L. Castro, J.R. Nair, F. Bella, F. Bardé, G. Meligrana, C. Gerbaldi, ACS Appl. Energy Mater. 2, 1600-1607 (2019)

M. Falco et al., Electrochem. Commun. 118 106807 (2020)

S. Saffirio, M. Falco, G.B. Appetecchi, F. Smeacetto, C. Gerbaldi, Journal of the European Ceramic Society, 42(3), 1023-1032 (2022).
Dilatometric Investigation of Si-Rich Contacting Anode Under External Pressure
Authors: Banifarsi Sanaz , Abdellatif Abdelaziz , Wohlfahrt-Mehrens Margret 
Published: February 2024

Silicon with high abundance and high gravimetric capacity around 3579 mAh.g-1 at Li15Si4 fully lithiated state [1] is one of the attractive anode materials in lithium-ion batteries. Volume expansion of around 300% in the fully intercalated state is the Achilles’ heel of silicon, causing particle pulverisation, continuous formation of solid electrolyte interface (SEI), loss of electrical contact and capacity loss.[2] The use of silicon composite instead of pure silicon, [1,3] limited de/lithiation,[4] and boosting the electrical connection between particles by applying optimal external pressure[5] are practical solutions to mitigate these disadvantages. This study investigates the electrochemical performance and the dilatometric behaviour of a multilayer pouch cells (0.06 to 1.5 Ah) under the external mechanical pressure. Using 1/3 of the Si capacity in order to stabilise the electrochemical performance of a high silicon content anode (70 wt% Si). An irreversible electrode expansion of about 20% after 3 cycles of formation at 0.1C and a 75% electrode thickening after 200 cycles at 0.5C were observed.

References

[1] P. Li, H. Kim, S.-T. Myung, Y.-K. Sun, Energy Stor. Mater. 35 (2021) 550–576. https://doi.org/10.1016/j.ensm.2020.11.028.
[2] L.Y. Beaulieu, K.W. Eberman, R.L. Turner, L.J. Krause, J.R. Dahn, Electrochem. Solid-State Lett. 4 (2001) A137. https://doi.org/10.1149/1.1388178.
[3] P. Kargl, V. Drews, P. Daubinger, O. Schweighofer, M. Marinaro, G.A. Giffin, M. Wohlfahrt-Mehrens, A. Thaler, J. Power Sources 548 (2022) 232042. https://doi.org/10.1016/j.jpowsour.2022.232042.
[4] M.N. Obrovac, L.J. Krause, J. Electrochem. Soc. 154 (2007) A103. https://doi.org/10.1149/1.2402112.
[5] M. Göttlinger, P. Daubinger, W. Stracke, S. Hartmann, G.A. Giffin, Electrochim. Acta 419 (2022) 140354. https://doi.org/10.1016/j.electacta.2022.140354.

Acknowledgment

Funding of the project HysKaDi (03XP0321) by the German Federal Ministry of Education and Research (BMBF) is gratefully acknowledged.

Figure 1