bluuebunny/crossref_metadata_2025_split huggingface dataset:
Combining Operando Techniques to Identify Challenges in Graphite Composite Negative Electrodes for Sulfide Based Solid-State Lithium Batteries
Authors: Hoeltschi Laura , Jordy Christian , Boillat Pierre , Cochet Magali , Villevieille Claire 
Published: February 2020

All-solid-state batteries are attracting growing attention as they have the potential for enhancing safety and electrochemical performances compared to conventional organic based batteries. Until now, among the available solid electrolytes, the sulfide based materials have presented the most interesting properties in terms of ionic conductivity and cold-pressing. Nevertheless, from DFT calculations it has been shown that their thermodynamic stability window is rather limited (lower than 1V) [1]. Chemical/electrochemical instabilities of the solid electrolytes towards graphite and high-voltage cathode materials are therefore reported. Currently, graphite is the state-of-the-art material for the negative electrode in commercial batteries because of its solid electrolyte interphase (SEI) stability, which allows graphite to be cycled with high capacity for a very long time and without significant fading. Unfortunately, its interfacial reaction with solid electrolytes is still unclear [2] [3]. The aim of this study is to identify the main parameters which need to be optimized to make the graphite electrode potentially viable in solid-state batteries in the near future.
First, the electrochemical performance of two electrolytes Li2S-P2S5 and LiI-Li2S-P2S5 have been tested in combination with graphite as composite negative electrode (50:50 wt.% ratio). Graphite materials with different particle sizes, surface areas and morphologies have been tested in a half-cell with a Li-In counter electrode. Long term cycling data of graphite with a sulfide-based electrolyte are depicted in Figure 1A. Afterwards, advanced operando techniques were employed to understand the capacity fading mechanism of graphite.
X-ray Tomography revealed initial cracks in the composite graphite electrode during the construction of the electrochemical test cell (see Figure 1B). Operando XRD showed that the graphite was not fully lithiated even during the first lithiation. Moreover, operando Neutron Imaging indicated that the electrode was more lithiated close to the separator than close to the current collector.
References
[1] Y. Zhu, X. He, Y. Mo, ACS Applied Materials and Interfaces 7, 23685-23693 (2015).
[2] K. Takada, T. Inada, A. Kajiyama, H. Sasaki, S. Kondo, M. Watanabe, M. Murayama, R. Kanno, Solid State Ionics 158, 269-274 (2003).
[3] Y. Kato, S. Shiotani, K. Morita, K. Suzuki, M. Hirayama, R. Kanno, Physical Chemistry Letters 9, 607-613 (2018).

Figure 1
Application of Solid State Nuclear Magnetic Resonance in Energy Storage Systems
Authors: Frerichs Joop Enno , Haneke Lukas , Li Meirong , Stan Marian Cristian , Winter Martin , Placke Tobias , Hansen Michael Ryan 
Published: February 2020

Since Sony introduced the Lithium Ion Battery (LIB) in 1991, an enormous effort has been made to further improve the performance of this battery system[1-2]. Nowadays, the research in LIBs is driven by the transition from combustion-based transportation to electric engines and the global energy revolution[3-5]. Environmental friendly cell chemistries are thus of particular interest in terms of recycling and safety reasons, especially for storage of renewable energies. In this connection, dual-graphite batteries receive increasing attention due to the use of graphitic carbon for both the negative and positive electrodes, i.e., free of transition metals[6]. A prerequisite for further improvements is clearly the understanding of the ongoing chemistry in these complex systems. In the last years, solid-state Nuclear Magnetic Resonance (NMR) has proven to be a very powerful technique for the investigation of the underlying chemistry of a vast number of materials used in LIBs[7-8]. Since NMR is not restricted to crystalline samples also highly disordered and amorphous materials can be studied. Furthermore, solid-state NMR provides quantitative measurements, is chemically specific and therefore extremely suitable for the investigation of the electrochemical processes in battery systems[7-8]. Also, the recent development of in situ or in operando measurements makes it highly beneficial for battery research[7-9]. In this contribution, we present the (i) first 119Sn NMR spectroscopic characterization of the Li-Sn system for the subsequent determination of Sn-containing battery materials, (ii) in operando determination of high surface area lithium (HSAL) on lithium metal electrodes, (iii) investigations of the charge/discharge mechanisms in S/PAN, and finally (iv) insights in the anion intercalation in dual-graphite cells.

References:

[1] J. Cabana, L. Monconduit, D. Larcher, M. R. Palacín, Advanced Materials
2010, 22, E170-E192.
[2] G. E. Blomgren, Journal of The Electrochemical Society
2017, 164, A5019-A5025.
[3] M. V. Reddy, G. V. Subba Rao, B. V. R. Chowdari, Chemical Reviews
2013, 113, 5364-5457.
[4] D. Andre, S.-J. Kim, P. Lamp, S. F. Lux, F. Maglia, O. Paschos, B. Stiaszny, Journal of Materials Chemistry A
2015, 3, 6709-6732.
[5] B. Scrosati, J. Garche, Journal of Power Sources
2010, 195, 2419-2430.
[6] T. Placke, A. Heckmann, R. Schmuch, P. Meister, K. Beltrop, M. Winter, Joule
2018, 2, 2528-2550.
[7] O. Pecher, J. Carretero-González, K. J. Griffith, C. P. Grey, Chemistry of Materials
2017, 29, 213-242.
[8] S. Haber, M. Leskes, Advanced Materials
2018, 0, 1706496.
[9] S. A. Kayser, A. Mester, A. Mertens, P. Jakes, R.-A. Eichel, J. Granwehr, Physical Chemistry Chemical Physics
2018, 20, 13765-13776.
Electrode, Electrolyte and Architecture Assessment for High Power Thin Film Microbatteries
Authors: McGrath Louise M , O'Donoghue Aaron , Clancy Tomas , Burke Micheal , Rohan James F. 
Published: February 2020

Silicon integrated on-chip energy storage is an attractive goal for hybrid power sources coupled with energy harvesting for ‘Internet of Things’ devices and applications. Typical thin film microbatteries are limited to low power and energy outputs in the 2D planar formats. One of the issues with solid-state thin film microbatteries is the high resistance of the electrolyte which can lead to significant potential drop when powering devices during sensor operation and communication. The ability to provide high currents in a small form factor is a critical need for the development of realistic long life devices.
In this work we will describe the use of Comsol finite element simulations to assess electrode materials, appropriate electrolytes and optimised architectures for improved microbattery power outputs. The simulations were of a microbattery stack where non-porous additive-free LiCoO2 is the cathode, lithium metal is the anode and solid-state, polymer, polymer-gel and liquid electrolytes were investigated. The simulations show the material utilisation and overall electrochemical cell behaviour of Li-ion electrode materials at typical and high power rates. Core-shell structures based on nanoarchitectures for electronic contact and active electrode materials have been investigated to improve power delivery for nanoscale active materials and for low conductivity oxide cathodes.
The simulations indicate that the implementation of nanoarchitectures such as 3D and 3D core-shell nanoarchitectures when coupled with the appropriate electrolytes and interfacial reactions can have a significant advantage in terms of areal energy and power capabilities compared to a thin-film geometry for a microbattery cell. The deployment of these architectures for microbatteries where area is at a premium and high power capabilities are desirable should result in better performing hybrid energy and less complex power management systems.

Acknowledgments

The authors would like to acknowledge the financial support from Science Foundation Ireland (SFI) Grant number: 12/IP/1722, Nanomaterials design and fabrication for energy storage. This work is supported in part by a research grant from SFI co-funded by the European Regional Development Fund under Grant Number 13/RC/2077. This work is also supported in part by a research grant from the EU Horizon 2020 work programme – Enables, European Infrastructure Powering the Internet of Things, project number 730957.
Photoelectrochemical and Surface Analysis of CdSe-Poma Composites on Highly Organized Pyrolytic Graphite
Authors: Dulovic Stephanie , Casto Sophia Maria , Widera Justyna , Maranowski Bartosz , Strawski Marcin , Szklarczyk Marek 
Published: February 2020

Over the past decade, semiconductors have been of great interest and currently found applications in computers, cell phones, and medical equipment. Semiconductors provide the basis for the operation of a solar cell in the study of the conversion of solar energy into electricity.
This study intended to analyze the stability and efficiency of semiconductor hybrid composites containing cadmium selenide (CdSe) and poly(o-methoxyaniline) (POMA), in the presence of light. The deposition of the CdSe-POMA composites was performed through electrochemical cycling on highly organized pyrolytic graphite (HOPG) surfaces. The composites differed in the order, in which the two components were deposited: (1) CdSe before POMA (CdSe/POMA), (2) POMA before CdSe (POMA/CdSe), and (3) CdSe and POMA simultaneously (CdSe+POMA). The CdSe/POMA and POMA/CdSe composites were deposited in their respective orders, with CdSe layer deposited for 20 cycles via cyclic voltammetry from the solution containing 5 mM CdSO4 and 1 mM SeO2 in 0.1 M HClO4, and POMA film polymerized for 5 cycles from the solution containing 0.06 M o-anisidine in 0.1 M HClO4. The deposition of CdSe+POMA was performed for 20 cycles via electrochemical cycling in the solution of 5 mM CdSO4 + 1 mM SeO2 and 0.06 M o-anisidine in 0.1M HClO4.
The photoelectrochemical studies of the created composites consisted of cyclic voltammetry, open circuit potentiometry and chronoamperometry were performed in the 0.1M Na2SO3 solution. The composite of CdSe/POMA presented the greatest photopotential around 220 mV, while POMA/CdSe (30 mV) and CdSe+POMA (14 mV) showed much smaller photopotential values. The chronoamperometric studies found that CdSe/POMA had the greatest photocurrent density of 17 μA/cm2, while POMA/CdSe (0.05 μA/cm2) and CdSe+POMA (0.42 μA/cm2) had substantially smaller photocurrent density. The POMA/CdSe and CdSe+POMA composites proved to be less stable and less photo-active. Following photostudies, the surface morphology and composition of these hybrids were analyzed using X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). The surface analysis found a greater degree of degradation of the other two composites (POMA/CdSe, CdSe+POMA), indicating that the polymer deposited above the CdSe layer in the CdSe/POMA composite may be crucial in lessening the degree of degradation resulting from the photo-exposure.
Modeling the Origin of the Interface Resistance in Solid-State Batteries
Authors: Qi Yue , Swift Michael , Tian Hong Kang 
Published: February 2020

The major bottleneck for the all-solid-state batteries lies at the high interfacial resistance, which is due to two main factors, physical contact and chemical effect, both will be evaluated via modeling in this talk.
First, we devise a model, incorporating atomic electrochemical potentials, thermodynamic stability of bulk electrolyte phases, and point defect formation energies to yield quantitative profiles of the electrostatic potential, lithium chemical potential, and electronic energy levels. This model complements direct microscopic and macroscopic simulations by rigorously and simultaneously determining the potential drop, electrostatic dipole, and space-charge layer at the interface. The application of this model to the Li/LiPON/LixCoO2 system leads to the important discovery that the space-charge layer varies with the state of charge (i.e. Li concentration in LixCoO2). This new physics insight unifies the seemingly contradictory experimental observations and leads to new device design rules to promote interfacial ion transport in future SSBs.
Secondly, we combined contact mechanics with 1D Newman battery model to capture the effect of imperfect electrode/electrolyte interfacial contacts, which can be formed during cell fabrication and worsened due to cycling. Constant current discharging processes at different rates and contact areas were simulated to correlate the capacity drop with the contact area loss. Furthermore, the model suggested how much pressures should be applied to recover the capacity drop due to contact area loss.
Surface Functionalization of Metal-Organic Framework Prior to TiO2 Tethering for Oxygen Reduction Catalysis in Alkaline Media
Authors: Grewal Simranjit , Macedo Angela , Lee Min Hwan 
Published: February 2020

Oxygen reduction reaction (ORR) is one of the most studied reactions for clean energy devices such as fuel cells and metal-air batteries due to its intrinsically sluggish kinetics which often limits device performance. Non-precious transmission metal oxides (TMO) such as Fe3O4, MnOx and Co3O4[1] have been intensively probed as alternatives to platinum-based catalysts. To supplement low electronic conductivity of TMOs, they are often dispersed on a highly conductive carbon nanostructure with a large surface area, maximizing catalytically active sites per volume and mass.
We employ a hybrid structure where both cobalt and cerium nitrate salts with a ligand called [1,1’-Biphenyl]-4,4’-dicarboxylic acid create an MOF (MOF-Ce-Co) with extreme surface area and excellent electronic conductivity using the hydrothermal process and pyrolysis. While this structure is conductive, its conductivity can be improved with the functionalization of cerium particles. Specifically, Ce(IV) complexes have been reported to show superior rates of phosphonate ester bond cleavage compared to other metal oxides. The unprecedented activity of Ce(IV) has been attributed to the role of the Ce(IV) 4f orbitals that can mix with the orbitals of the P=O bond to form hybrid orbitals[2]. To functionalize cerium, phosphoric acid is used to bind a phosphate group onto cerium oxide. This gives rise to a penta-coordinate intermediate that is susceptible to a nucleophilic attack[2]. The treated MOF-Ce-Co is then hydrothermally reacted (at 160 ºC for 24 h) with the precursor P25, thus creating MOF-Ce-Co with TiO2 attached.
Results have indicated that phosphate groups not only absorb cerium nanoparticles, but TiO2 thus resulting in enhance performance in terms of current density, and onset/half-wave potential as seen in both CV and LSV data. FT-IR results indicate that an absorption of 1040 cm-1 (corresponding to a phosphate group) appeared once MOF-Ce-Co was treated with phosphoric acid. An X-ray analysis showed that both samples (MOF-Ce-Co and MOF-Ce-Co with TiO2) had cerium and cobalt particles, however, MOF-Ce-Co with TiO2 had an additional peak at 56º, indicating that presence of TiO2 (Anatase). Hence, the improved performance of the treated MOF is the result from functionalization.
This project was funded by NASA Advanced STEM Training and Research (ASTAR) Fellowship.
References:
[1] G. Wu and P. Zelenay, “Nanostructured nonprecious metal catalysts for oxygen reduction reaction.,” Acc. Chem. Res., vol. 46, no. 8, pp. 1878– 89, Aug. 2013.
[2] T. Islamoglu, A. Atilgan, S. Moon, G. Peterson, J. DeCoste, M. Hall, J. Hupp, and O. Farha, "Cerium(IV) vs Zirconium(IV) Based Metal-Organic Framwork for Detoxification of a Nerve Agent." Chemistry of Materials., vol. 29, no. 7, pp. 2672-2675, May 2017.

Figure 1
Study of SEI Components Enabling Calcium Metal Plating and Stripping
Authors: Forero-Saboya Juan , Yousef Ibraheem , Davoisne Carine , Dedryvère Rémi , Canepa Pieremanuele , Ponrouch Alexandre 
Published: February 2020

Due to serious concerns about future availability and price increase of lithium minerals, several alternatives have been investigated to substitute lithium-ion batteries in high demand applications. Divalent-cation chemistries, such as calcium and magnesium, promise a high energy capacity relying on much more abundant elements (5th and 8th, respectively, in the earth crust) than lithium (25th). Until recently, the development of such battery concepts was focused on electrolytes that do not form passivation films (solid electrolyte interphases - SEI) on the metal surface [1]. These electrolytes, however, suffer from a low stability towards oxidation and thus, limit the output voltage of the assembled cells.
Previous works from our group demonstrated calcium plating and stripping in SEI-forming electrolytes at moderate temperatures [2]. Specifically, redox activity of calcium metal was observed in a Ca(BF4)2 electrolyte dissolved in a mixture of cyclic carbonates, while no activity was observed when TFSI was used as anion.
The current study focuses on understanding the chemical composition differences between the SEI layers formed in the two systems analysed. A systematic characterization of the SEI formed on the Ca metal anode in various electrolyte formulations will be presented and the most suitable SEI compounds in terms of divalent cation mobility will be discussed.
References
[1] J. Muldoon, C. B. Bucur and T. Gregory, Chem. Rev., 2014, 114, 11683–11720.
[2] A. Ponrouch, C. Frontera, F. Bardé and M. R. Palacín, Nat. Mater., 2016, 15, 169–172.
(Invited) Beneficial Effect of Fsi-Based Electrolytes on Capacitor Performance
Authors: Ishikawa Masashi , Uchida Satoshi , Hirota Naoya 
Published: February 2020

A lithium ion capacitor (LIC) is an electric energy storage device that combines an electric double-layer capacitor (EDLC) with a lithium ion battery (LIB). Although LIC features an excellent power density like EDLC, the energy density of LIC is lower than that of LIB. Therefore, improvement of energy density is required for LIC. In the present study, to achieve high energy density of LIC, porous 3-dimensinal (3-D) current collector is applied to LIC electrodes. This 3-D current collector can increase the packing density of active material. It is, however, expected that diffusion of ionic carriers is limited when using conventional organic electrolytes because electrodes based on the 3-D current collector should be massive. As a result, LIC using the 3-D current collector may deliver limited power. Here bis(fluorosulfonyl)imide (FSI)-based ionic liquids (ILs) that have high carrier density would be useful as an electrolyte for LIC to maintain power. The purpose of this study is applying an FSI-based IL electrolyte to LICs with porous 3-D current collector.
We assembled a three-electrode cell. A positive electrode using aluminum 3-D current collector was composed of activated carbon, acetylene black (AB) and polyvinylidene di-fruoride (PVdF). A negative electrode using copper 3-D current collector was composed of hard carbon, AB and PVdF. A lithium foil was used as a counter electrode and reference electrode. We used LiFSI/EMImFSI as an IL electrolyte. The cell was charged and discharged for 3000 cycles at 1.0 C-rate in a voltage range of 2.0 – 3.8 V. We also evaluated rate performance of the LIC cells by rapid charging and discharging test up to 30 C-rate.
Potential profiles of positive and negative electrodes were observed during charge and discharge at the 2nd, 1000th and 3000th cycles. It turns out that the LIC cell containing the IL electrolyte can be charged and discharged reversibly as well as stably. Even though a test was long-term cycling such as 3000 cycles, the capacity has not significantly decreased. We compared rate performance among the IL electrolyte and two organic electrolytes. Although ILs have high viscosity, it is shown that the FSI-based IL electrolyte has high rate performance comparable to that of a LiPF6-based organic electrolyte. This may be ascribed to high carrier density of the IL. These results suggest that applying the IL electrolyte to a LIC electrode with the porous 3-D current collector is promising to keep or enhance energy and power capability.
We will also report the effect of FSI-based electrolytes including IL systems and solvent-based ones on the charge-dicharge performance of EDLCs.
(Invited) Investigating the Hydrogenase Mechanism By Protein Film Electrochemistry
Authors: Ceccaldi Pierre , Berggren Gustav 
Published: February 2020

With turnover frequencies up to 106 s-1, hydrogenases are the fastest molecular hydrogen catalyst. They are classified according to the metal content of their active, distinguishing the NiFe and FeFe as the two major classes. The two classes display an outstanding organometallic cofactor, with cyanido- and carbonyl- groups coordinating the metals. Their mechanism includes the stabilization of a metal-hydride state as the most reduced intermediate of the catalytic cycle. Hydrogenase (Hase) have driven mechanistic studies for decades, including extensive works by protein film electrochemistry targetting aspects as diverse as intramolecular diffusion of gases, long distance electron transfer, or susceptibility to inhibitors. This communication will focus on two other questions, distinguishing steady state functioning and in-activation processes (see figure).
The catlaytic bias is the ability of an enzyme to turnover faster one direction than another. Amongst hydrogenases, the catalytic bias spans full range, from extremely biased to essentially neutral enzymes. Several works have brought clues to understand the molecular basis of the catalytic bias for both Hase classes, pointing out to the intramolecular electron transfer chain as the main effector. Our recent results on the study of the hydrogen dependent CO2 reductase reveal the role of the affinity for hydrogen in the bias.
The susceptibility to overpotential corresponds to in-activation processes triggered by redox conditions that are far from equilibrium, and plausibly encountered in the life cycle of bioelectrochemical devices. One particular phenomenon is the reductive inactivation of FeFe-Hases, undergoing both in solution and on the electrode, that remains largely to understand. Our works on the enzyme HydA1 from microalgae suggest that this inactivation can be reversed under maintained reductive conditions, unlike discussed in the literature.

Figure 1