bluuebunny/crossref_metadata_2025_split huggingface dataset:
Potential of Knudsen Effusion Mass Spectrometry (KEMS) for Energy Materials Science
Authors: Markus Torsten , Henriques D. 
Published: February 2024

The determination of valuable thermodynamic data for materials at elevated temperatures is a very important issue in Materials Science. This can be achieved by the elucidation of vaporization processes with mass spectrometric techniques.
Knudsen Effusion Mass Spectrometry provides the identification of gaseous species present above condensed phases and permits the determination of their partial pressures up to a total pressure of 200 Pa.
The key for establishing model calculations using DG minimization tools like among others FactSage, Pandat or Thermocalc is the knowledge of the thermodynamic data of molecules and compounds. This includes the partial pressures of gaseous species, the standard enthalpies and entropies of formation of gaseous and condensed phases as well as their enthalpies and entropies of mixing and the knowledge of phases and chemical compounds which are formed upon reactions.
The method will be described and examples and an insight will be given how basic thermodynamic data are derived with the above mentioned method for the incorporation into thermodynamic databases. Examples of investigations carried out in our lab will be given.
The number of groups worldwide using this advanced technology has been shrinking during the last decades. Therefore, we are pleased to announce the setup of a completely new designed instrument in our laboratory which can determine data with higher precision and better resolution.
The new set up will be presented as well.
(Invited) Exploiting Organic Materials for Next Generation Batteries
Authors: Meabe Leire , Aldalur Itziar , Arrese-Igor Mikel , Boaretto Nicola , Armand Michel , Sanchez-Diez Eduardo , Martinez-Ibañez María , Ortiz-Vitoriano Nagore 
Published: February 2024

Energy storage plays, undoubtedly, a fundamental role in the process of total decarbonization of the global economy that is expected to take place in the coming decades. The energy transition to a renewable and sustainable generation will be the solution to reduce greenhouse gas emissions and thus achieve the European Commission´s goal of becoming the world´s first decarbonized economy. Our mission is therefore aligned with this goal by improving the industry competitiveness and sustainable development, from a benchmark position in energy research, generating disruptive knowledge in materials and high-tech solutions. Within the electrochemical storage area, and in particular organic hybrid materials group, we work from the synthesis and design of organic molecules and polymeric materials to the understanding of their properties and interfaces with the ultimate goal of developing next generation battery systems.
In this talk, a general overview of our core research will be given with a special focus on the design of polymer electrolytes. In recent years we have explored various strategies to meet the requirements of electrolytes: high lithium cation conductivity and stability against high voltage and towards lithium metal (LiM). In this scenario we have synthesized new polymers and lithium salts. Inspired by poly(ethylene oxide), polymers containing ethylene oxide units will be presented, with decreased crystallinity to improve ionic conductivity.1 This improvement generally compromises the mechanical properties. In this respect, different strategies will be shown.2,3 However, it is difficult to design a polymer that meets all properties. In this scope, a bi-layer concept will be described and how salt migration can be addressed using a single-ion conducting polymer electrolyte (SLIC).4,5 Motivated by the bi-layer strategy, within SAFELiMOVE EU project a new solid-state-based technology have been proposed.6 The most relevant work carried out in the framework of the project will be presented.
References

I. Aldalur et al., J Power Sources, 347, 37–46 (2017).

I. Aldalur et al., J Power Sources, 448, 227424 (2020)

I. Aldalur, M. Martinez-Ibañez, M. Piszcz, H. Zhang, and M. Armand, Batter Supercaps, 1, 149–159 (2018)

M. Arrese-Igor et al., ACS Energy Lett, 7, 1473–1480 (2022)

M. Arrese-Igor et al., Energy Storage Mater, 45, 578–585 (2022)

https://safelimove.eu/
Effect of Particle Size Ratio on Microstructure and Active Material Utilization in Argyrodyte All-Solid-State Composite Cathodes
Authors: Steckermeier Dominik , Gerstenberg Jessica , Hartmann Elisa , Michalowski Peter , Kwade Arno 
Published: February 2024

Among next-generation batteries, all-solid-state batteries (ASSB) promise increased energy densities, fast charging properties, and higher safety compared to traditional liquid-based systems. To achieve the demanded high energy densities high mass loadings of the composite cathodes are necessary. These consist of active material (AM), solid electrolyte (SE), and conductive additive as well as binder. Volume changes of intercalation AM and insufficient ionic percolation at low SE contents lead to an increased interfacial resistance and capacity loss. In order to promote cathode AM utilization the particle size ratio of the AM and the SE within the composite cathode needs to be optimized.
Theoretical calculations have shown that for high AM utilization at high AM loadings particle size ratio is a crucial parameter [1, 2]. Experimentally, the influence of particle size ratio has so far only been studied at laboratory scale. However, scalable process routes have not considered this important aspect. In this work, we present a solvent-based process route for the preparation of sulfide-based solid-state composite cathodes with NCM622 as AM, starting from the adjustment of the particle size of a commercially available Li6PS5Cl SE by planetary ball mill. Further process steps include the dispersion of SE with AM and conductive additive and doctor blade coating of cathode films. We analyzed the composite cathodes with regard to their internal resistance as well as their microstructure and conducted electrochemical tests in lab-scale test cells. Optimization of the particle size ratio results in an increase of AM utilization by a factor of 5 as well as an enhanced AM-SE-particle contact area and lower porosity.
References
[1] Shi T, Tu Q, Tian Y, et al. High Active Material Loading in All‐Solid‐State Battery Electrode via Particle Size Optimization. Adv. Energy Mater. 2020; 10(1): 1902881
[https://doi.org/10.1002/aenm.201902881]
[2] Bielefeld A, Weber DA, Janek J. Microstructural Modeling of Composite Cathodes for All-Solid-State Batteries. J. Phys. Chem. C 2019; 123(3): 1626–34
[https://doi.org/10.1021/acs.jpcc.8b11043]
Contribution of Anode and Cathode Potentials during Charging to the Performance of Aluminium-Ion Battery with Triethylamine-AlCl3 Electrolyte
Authors: Mukundan Charan , Drillet Jean-Francois 
Published: February 2024

Aluminium ion batteries (AIBs) are a promising emerging battery technology, thanks to the high theoretical gravimetric and volumetric energy density of Aluminium as well as its very large abundancy and recycling capability.[1] In aprotic graphite-Al cell, however, practical energy density is limited by both electrochemical stability window of the electrolyte (2.4-2.6V) and specific capacity of graphite for long-term reversible storage of large AlCl4
- anions (radius 530 pm vs. 68 pm for Al3+). This works aims at studying the influence of cut-off voltage value during charging step in 1:1.5 triethylamine hydrochloride / aluminium tetrachloride (TEA:AlCl3) electrolyte on Al and graphite electrode potential under half-cell and full-cell conditions.
In Aluminium symmetric cell, potentials during Al deposition on an Al foil at 1 mA cm-2 were 60-70 mV higher in TEA-AlCl3 electrolytecompared to the cell measured with EMIMCl-AlCl3 electrolyte as reference system. Because of higher electrochemical stability of TEA-AlCl3 solution than EMIMCl-AlCl3 electrolyte, cut-off voltage of charging step in AIB full-cell was set to 2.45 V compared to 2.40 V for the reference cell. During long-term cycling at 1 A g-1, the specific capacity of the AIB cell employing TEA-AlCl3 increased from 60to 94 mAh g-1 (57%) after 1000 cycles while that of cell with EMIMCl-AlCl3 was quite constant at about 60 mAh g-1. This behaviour was explained by continuous decreasing in Al electrode potential at End-of-Charge state (EOC) during deposition reaction (charging step) in TEA-AlCl3 allowing an increase in graphite electrode potential and consequently in AIB cell capacity over the whole experiment. This increase in capacity was also accompanied by a raise of defect sites in graphite material which was revealed using Raman spectroscopy.
(Invited) Potassium-Ion Batteries
Authors: Pasta Mauro 
Published: February 2024

Potassium-ion batteries (KIBs) are emerging as a promising complementary technology to lithium-ion batteries due to their potential low cost and high-rate capability [1].
In my talk, I will discuss the progress our group has made in understanding the structure-electrochemistry relationship of Prussian Blue analog cathodes [2–5]; the electrochemomechanical properties of red phosphorous (RP) [6] and their application in RP-graphite composite anodes [7] , and the transport and thermodynamic properties of K-ion electrolytes [8]. I will then highlight the critical research challenges that need to be addressed for KIBs to be commercialised[1].

References

[1] S. Dhir, S. Wheeler, I. Capone, M. Pasta, Chem
2020, 6, 2442–2460.
[2] J. Cattermull, M. Pasta, A. L. Goodwin, Materials Horizons
2021, 8, 3178–3186.
[3] J. Cattermull, K. Sada, K. Hurlbutt, S. J. Cassidy, M. Pasta, A. L. Goodwin, Chem. Mater.
2022, 34, 5000–5008.
[4] K. Hurlbutt, S. Wheeler, I. Capone, M. Pasta, Joule
2018, 2, 1950–1960.
[5] M. Fiore, S. Wheeler, K. Hurlbutt, I. Capone, J. Fawdon, R. Ruffo, M. Pasta, Chem. Mater.
2020, 32, 7653–7661.
[6] I. Capone, J. Aspinall, E. Darnbrough, Y. Zhao, T.-U. Wi, H.-W. Lee, M. Pasta, Matter
2020, 3, 2012–2028.
[7] I. Capone, J. Aspinall, H. J. Lee, A. W. Xiao, J. Ihli, M. Pasta, Materials Today Energy
2021, 21, 100840.
[8] S. Dhir, B. Jagger, A. Maguire, M. Pasta, Research Square
2022.

Figure 1
Inorganic Ultra-Rich Solid Composite Electrolytes for High-Voltage Solid-State Batteries
Authors: Vattappara Kevin , Finsterbusch Martin , Fattakhova-Rohlfing Dina , Kvasha Andriy 
Published: February 2024

Solid-state batteries (SSB), in which flammable organic liquid electrolytes are replaced by inherently safer solid electrolytes (SEs), are considered to be the evolution of current Li-ion battery technology toward greater safety and higher energy density. Among the various SEs, the PEO-LiTFSI system has been the most studied due to its low cost and ease of processing. However, the relatively low oxidation stability of PEO-LiTFSI at about 4.0 V vs. Li/Li+ does not allow the use of high-voltage cathode active materials, which limits the available energy density [1]. We propose that a high content of Li-ion conductive ceramic in the PEO-LiTFSI matrix increases oxidation stability, allowing stable cell cycling with Ni-rich NMC cathode at higher voltages. This class of inorganic ultra-rich composite SEs has attracted much interest recently [2, 3].
In this work, we present a self-standing, dense, flexible (Fig.1a), and thermally stable (Fig.1b) composite solid electrolyte (INURSE 30) that has an ultra-high content of Li-ion conductive LLZO (90 wt%, as confirmed by TGA in Fig. 1b)in the PEO-LiTFSI matrix. The ionic conductivity of INURSE 30 is 1.4x10-5 S/cm at 60ºC. The INURSE 30 electrolyte shows long-term cycling stability of more than 2000 h at a current density of 0.01 mA/cm2 in symmetric cells with Li electrodes. In addition, the high-voltage stability of INURSE 30 was demonstrated in solid-state cells with a composite solid-state cathode containing 75 wt% NMC622 and a Li metal anode. The Li/INURSE 30/NMC622 coin cell shows good coulombic efficiency and capacity retention, as shown in Fig.1c.

K.V. acknowledges the financial support from Fundacíon CIDETEC and DESTINY PhD programme which received funding from the European Union's Horizon2020 research and innovation programme under the Marie Skłodowska-Curie Actions COFUND - Grant Agreement No: 945357.

References:
[1] M. Wetjen, G.T. Kim, M. Joost, G.B. Appetecchi, M. Winter, and S. Passerini, J. Power Sources (2014) 246, pp.846-857.
[2] C. Wang, Y. Yang, X. Liu, H. Zhong, H. Xu, Z. Xu, H. Shao, F. Ding, ACS Appl. Mater. Interfaces, (2017) 9, 15, 13694–13702.
[3] Q. Guo, F. Xu, L. Shen, S. Deng, Z. Wang, M. Li, X. Yao, Energy Mat. Adv. (2022) 9753506, DOI: 10.34133/2022/9753506.

Figure 1
Towards an in-Depth Understanding of Single-Ion Conducting Polymer Electrolytes for Lithium-Metal Batteries
Authors: Mayer Alexander , Bresser Dominic 
Published: February 2024

Recently, we have reported a new polyarylene-based single-ion conducting multi-block copolymer electrolyte providing very high ionic conductivities of about 1 mS cm-1 at ambient temperature and excellent cycling stability of LiNMC811 (LiNi0.8Mn0.1Co0.1O2) cells – even at 0 °C.1–3 Further improvement of this new electrolyte system, however, requires an in-depth understanding of ideally each single functional unit in the polymer.
Herein, we present some of our latest results on the experimental and theoretical investigation of stepwise modified copolymers in order to decipher the impact of the different functional groups on the eventual mechanical, thermal, chemical, and electrochemical behavior. This stepwise modification includes, amongst others, the replacement of the biphenyl unit by a series of bisphenol derivatives and the variation of the ionophobic and ionophilic block. The former approach provides the unique opportunity to investigate the influence of the monomer substitution pattern, while the latter unveils some rather unexpected findings concerning the impact of the lithium concentration in the electrolyte.

References

H.-D. Nguyen et al., Energy Environ. Sci., 11, 3298–3309 (2018).

D. Steinle et al., J. Solid State Electrochem., 26, 97–102 (2022).

Z. Chen et al., Nano Energy, 77, 105129 (2020).
Increasing the Sodium Content in P2-Type Layered Oxides As Cathode Materials for Sodium-Ion Batteries
Authors: Xu Mingfeng , Bianchini Matteo 
Published: February 2024

P2-type layered oxides exhibit superior Na ion conductivity and structural stability compared to their O3 analogues, making them promising candidate materials for next generation batteries. However, their lower initial Na contents (Na/transition metals < 1) restrict their capacity during the first charge process, and the transitions between P- and O2-type structures during cycling further deteriorate their stability.[1,2]

Our work aims to increase the Na inventory in pristine cathode compositions, especially relevant for full cell systems, while maintaining their cycling stability. We started with the well-studied P2 material Na2/3Ni1/3Mn2/3O2 and have worked on incorporating Li in the transition metal layers to stabilize the structure, while at the same time increasing the Na content.[3,4] In this respect, a great challenge is to control the phase formation during the synthesis. When the Na content exceeds a certain limit, an O3 structure is more likely to form than a P2 structure.[1] On the other hand, at too low temperatures, a P3 polymorph is preferred.[5] By regulating the synthesis conditions, Na contents have been successfully increased in a series of materials between two end compositions, Na2/3Ni1/3Mn2/3O2 and Na5/6Li5/18Mn13/18O2.
In this presentation, we report on unpublished in situ XRD characterizationsof these compositions during their solid-state synthesis, as well as on their crystal structures and electrochemical behavior, which involves varying amount of Ni redox. These time-resolved studies of structural evolutions provide guidance for further synthesis of desired phases and compositions. Along with the electrochemical results, we also aim to answer the questions on the charge compensation mechanisms that sustain the electrochemical performance as the amount of Li increases and Ni decreases. Finally, we also explore which amount of Li substitution can best balance the structural stability and capacity retention of the cathode material.
References
[1] C. Zhao, Q. Wang, Z. Yao, J. Wang, B. Sánchez-Lengeling, F. Ding, X. Qi, Y. Lu, X. Bai, B. Li, H. Li, A. Aspuru-Guzik, X. Huang, C. Delmas, M. Wagemaker, L. Chen, Y.-S. Hu, Science
2020, 370, 708–711.
[2] D. H. Lee, J. Xu, Y. S. Meng, Phys. Chem. Chem. Phys.
2013, 15, 3304.
[3] T. Jin, P. Wang, Q. Wang, K. Zhu, T. Deng, J. Zhang, W. Zhang, X. Yang, L. Jiao, C. Wang, Angew.
Chem. Int. Ed.
2020, 59, 14511–14516.
[4] J. Xu, D. H. Lee, R. J. Clément, X. Yu, M. Leskes, A. J. Pell, G. Pintacuda, X.-Q. Yang, C. P. Grey, Y. S. Meng, Chem. Mater.
2014, 26, 1260–1269.
[5] M. Bianchini, J. Wang, R. J. Clément, B. Ouyang, P. Xiao, D. Kitchaev, T. Shi, Y. Zhang, Y. Wang, H. Kim, M. Zhang, J. Bai, F. Wang, W. Sun, G. Ceder, Nat. Mater.
2020, 19, 1088–1095.
Interfacial Chemistry in Aqueous Lithium-Ion Batteries with Dilute Aqueous Electrolytes: A Case Study with V2O5
Authors: Hou Xu , Zhang Leiting , Gogoi Neeha , Edström Kristina , Berg Erik J. 
Published: February 2024

Aqueous lithium ion batteries (ALIBs) are promising candidates for large-scale energy storage systems, benefiting from the intrinsic safe and environmentally friendly properties of aqueous electrolytes. However, its practical application is impeded due to the narrow electrochemical stability windows (ESWs) of aqueous electrolytes. Despite that increasing electrolyte concentration can achieve a wide ESW with the protection of SEI layer, it brings numerous disadvantages induced by excessive salt as well. Therefore, understanding the SEI formation mechanism and further widening the ESWs of dilute aqueous electrolytes are critical for the breakthrough of next-generation ALIBs.
Herein, the interphase chemistry of V2O5 electrode with dilute aqueous electrolyte was systematic investigated by conducting various Operando characterizations with LMO||V2O5 cell system. Dynamic SEI, which consists of Li2CO3, LiF and V2O4, was formed during charge and disappeared during the following discharge, which is strongly affected by electrolyte pH fluctuation. Moreover, its evolution process is reversible during cycling. There are several impacts affect the pH fluctuation during cycling. First, V2O5 dissolution, which turns electrolyte into acidic before cycling, and is aggravated by electrolyte concentration decrease. Second, proton/hydronium ion insertion, which takes place on electrode surface in dilute electrolyte, while it is suppressed by concentration increase due to reduced proton concentration. Third, the redox reaction of dissolved V2O5, which is controlled by both potential and electrolyte pH change according to the V-H2O poubaix diagram. Along with the anode potential decrease and the alkalinisation of electrolyte, V2O4 is formed on anode surface by the reduction of HV10O28
5- and V4O12
4- and this reduction process further produces hydroxide ion into electrolyte. Last, the carbon oxidation, which takes place on cathode side during charge and on anode side during the final discharge. Therefore, the acidification of electrolyte during cycling is detrimental to SEI stability in aqueous electrolytes. This systematic research work provides new perspectives to the understanding of the interphase chemistry evolution in aqueous Li-ion batteries using dilute electrolytes, which guides the building of effective SEI layer in aqueous Li-ion batteries and beyond.

Figure 1
First-Principles Calculations on Diffusion and Association Behavior of Fluoride Ions in Ba-Doped LaF3 Solid Electrolyte
Authors: Kuwabara Akihide , Ogawa Takafumi , Fisher Craig , Moriwake Hiroki , Ikuhara Yuichi 
Published: February 2024

Fluoride ion batteries, which generate electrical energy through the fluorination/de-fluorination reaction of electrode active materials, are expected to be the next-generation storage batteries with high energy density. LaF3 with a tysonite-type structure is known as one of the representative solid-state fluoride ion conductors. Substitutional solid solution of divalent cations such as Ba or Sr ions at La sites forms fluoride ion vacancies as charge compensation, resulting in fluoride ion conductivity. The main objective of this study is to analyze the formation behavior of point defects in LaF3 through quantitative evaluation of their formation energies using first-principles calculations, and to elucidate the conduction mechanism of fluoride ions in LaF3.
The plane-wave basis PAW method implemented in VASP code was used for the electronic structure calculations. The electron correlation treatment uses the PBEsol-type potential based on the generalized gradient approximation. Calculations for given point defects were performed. The cutoff energy of the plane wave basis sets was set to 420 eV, and the structure optimization calculations were performed until the Hellmann-Feynman force acting on each atom was less than 0.02 eV/Å.
There are three fluoride ion sites (12g, 4d, and 2a) in the unit cell of LaF3. Using the supercell model, we calculated the defect formation energies of fluoride ion vacancies at each site. The formation energies at the 12g, 4d, and 2a sites are 0.17 eV, 0.52 eV, and 0.52 eV, respectively. According to the defect formation energies, fluoride ion vacancies are most likely to form at the 12g sites.
To elucidate the elementary processes of fluoride ion transfer between 12g sites by the vacancy mechanism, we performed first-principles calculations and transition state search using the Nudged Elastic Band method. From symmetry, four different pathways exist in the lattice of undoped LaF3. The pathway with the highest energy barrier is shown to have very low transfer energies, 0.17 eV, and the energy barriers of the other pathways are less than 0.1 eV. These results suggest that LaF3 has a potential for very fast fluoride ionic conductivity by the vacancy mechanism. In the presentation, the mechanism of fluoride ion conduction in Ba-doped LaF3 will also be reported.
This work was supported by the RISING2 (JPNP16001) and the RISING3 (JPNP21006) projects from the New Energy and Industrial Technology Development Organization (NEDO), Japan.