bluuebunny/crossref_metadata_2025_split huggingface dataset:
Interfacial Challenge for Solid-State Lithium Batteries- Liquid Addition
Authors: Yan Shuo , Yim Chae-Ho , Merati Ali , Baranova Elena A. , Abu-Lebdeh Yaser , Weck Arnaud 
Published: September 2023

All solid-state lithium batteries with garnet electrolytes (Li7La3Zr2O12, LLZO) are promising energy storage devices that have gained increasing attention due to their huge potential towards non-flammability and higher energy density. However, reported solid-state lithium batteries cannot achieve the projected energy density (> 500 Wh/kg at the cell level) mainly due to insufficient contact and poor compatibility between LLZO and electrodes. The use of liquid electrolytes in small quantities has been suggested as a component in the quasi-solid hybrid electrolytes to address these two issues. However, the working principle of liquid electrolytes added as the interface inside the batteries is not clear yet.
This study added 10L carbonate-based liquid electrolyte between LLZO and LiNi0.6Mn0.6Co0.2O2 (NMC 622) cathode. The assembled Li|LLZO|NMC 622 cell exhibited an initial discharge capacity of 168 mAh g-1 with a capacity retention ratio of ~82 % after 28 cycles. Scanning Transmission X-ray Microscopy revealed the reaction of LE with garnet and NMC 622. More importantly, the LE decomposed and solidified during the cycling process. Decomposed LE participated in the formation of a newly-identified solid-liquid electrolyte interface (SLEI) just after the 1st cycle. Furthermore, the X-ray Absorption Spectroscopy results indicated that the SLEI consisted predominantly of LiF, LaF3, Li2O, and Li2CO3 species.
Overall, this study proved the solidification of liquid electrolytes at the garnet/cathode interface. The formation of SLEI effectively suppressed the degradation of the garnet electrolyte and stabilized the battery cycling performance. More efforts are required to optimize the liquid and establish a more stable SLEI that could expand the cycling life of the batteries.
Electrochemical Stability of Electrode/Electrolyte Interfaces in Metal Borohydride Solid Electrolytes
Authors: Ko Matthew , Li Yiliang , Mair Sunil , Zhang Duhan , Chiang Yet-Ming 
Published: September 2023

Meeting the promise of all-solid-state batteries will require solid electrolytes that have high metal ion conductivity, low electronic conductivity, are electrochemically stable at both low and high potential, and have sufficiently high critical current density to avoid metal dendrite penetration. Metal borohydrides comprise a relatively new class of compounds that is being explored for its potential as a solid electrolyte material. Here, we examine the electrochemical thermodynamic stability of sodium amide borohydride (Na2NH2BH4, or NNB) over the potential range 1.5 to 5 V vs. Na/Na+, using electrodynamic methods, X-ray photoelectron spectroscopy (XPS) characterization of the interfacial reaction products1, and electron microscopy characterization of microstructure. We observe the formation of a CEI layer that passivates the NNB electrolyte up to 5V, while the electrolyte is stable without needing additional passivation down to potentials as low as 1.5V. The onset potentials of the CEI formation reactions agree with those predicted by DFT2 and suggest that the resulting CEI is composed of closo-borohydrates, which are a type of metal borohydride with a cage-like structure that holds promise for high sodium ion conductivities3. XPS measurements of atomic compositions in the CEI layer show the formation of these closo-borohydrates and, coupled with charge transfer calculations, predict that the passivating CEI layer is thin (tens of nm). Impedance spectroscopy is performed to characterize the contribution of the CEI layer to the total cell resistance. Several formation cycling methods are explored to show that with appropriate cycling, the passivating layers contribute <10% to electrolyte resistance in the test cells.

Acknowledgements: This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

References

[1] Tushar Swamy, Xinwei Chen, and Yet-Ming Chiang, “Electrochemical Redox Behavior of Li-ion Conducting Sulfide Solid Electrolytes,” Chem. Mater.,
31[3] 707-713 (2019)
[2] V. Lacivita, Y. Wang, S.H. Bo, G. Ceder. Ab initio investigation of the stability of electrolyte/electrode interfaces in all-solid-state Na batteries. J. Mater. Chem. A, 7., (2019) 7941-8654.
[3] T. J. Udovic, M. Matsuo, A. Unemoto, N. Verdal, V. Stavila, A. V Skripov, and J. J. Rush, “Sodium Superionic Conduction in Na2B12H12,” Chem. Comm.,
50 3750–3752 (2014)
Insights on Solid-electrolyte/electrode interfaces of All-solid-state Batteries: Multiscale Framework
Authors: Mamme Mesfin Haile , Bekaert Lieven , Gebregeorgis Tewelde , De Proft Frank , Hubin Annick , van Duin Adri 
Published: September 2023

The harmonious transition of society towards carbon-free technologies, from fossil fuel to renewable energy sources only, including transition from combustion engined cars to electrical vehicles, requires efficient and safe energy storage technologies [1-3]. Among the various battery technologies being available today, all-solid-state batteries (ASSBs) have garnered a lot of attention, due to their many advantages, including the high thermal stability, non-flammability, long lifetime. Moreover, they enable the use of lithium metal anode (theoretical specific capacity 3862 mAh g-1), which would increase considerably the performance of the ASSBs [4,5]. However, the realization of ASSBs is hampered by a limited understanding of the nanometer-thin solid-state electrolyte/electrode buried interfaces. In this talk, we present our recent findings and theoretical developments on the nanometer-thin solid-state electrolyte and electrode interfaces of solid state electrolyte in combination with different anode and cathode electrode interfaces. By combining a multiscale framework (DFT, reactive force field to continuum scale) with surfaces and electrochemical techniques (including Electrochemical Impedance Spectroscopy), the structural origin of interfacial resistance, the degradation mechanisms, and the lithium-ion transport mechanism at the cathode interfaces at different working/environmental conditions (Electric field, temperature, state of charge, etc.) are now better understood. As a result, the strategy of a hybrid multiscale experimental and computational framework paves the way towards further understanding and (re-)designing highly compatible and stable
electrolyte/electrode interfaces, which can be extended to other energy conversion and storage devices. Some of the findings will be discussed during the presentation.
References
1. K. Dahal, et al., Sustain. Cities and Soc., 2018, 40, 222.
2. V. Stamenkovic, et al., Nat. Mater., 2017, 16, 57.
3. M. Whittingham, MRS Bull., 2008.
4. K. Takada, et al., ACS Energy Lett., 2018, 3, 98.
5. A. Zhamu, et al., Energy Environ. Sci., 2012, 5, 5701.
(Invited) Unification of Bulk Storage and Supercapacitive Storage
Authors: Xiao Chuanlian , Usiskin Robert , Maier Joachim 
Published: September 2023

In typical insertion electrodes for batteries, the capacity is determined by bulk storage within the electroactive particles, which is comparatively well investigated and understood. In contrast, supercapacitor electrodes are dominated by interfacial storage at interfaces, which is well addressed experimentally. However the charge carrier chemistry (defect chemistry) especially in the latter case is not taken seriously. Consequently a bridge between the two important fields is absent. Following and extending our quantitative concept of job-sharing storage, a generalized description that includes bulk and space charge storage (electrochemical and supercapacitive storage) is possible. In other words the treatment of defect chemistry as a function of the degree of storage as well as of position is key to a unification.
The experimental part of our research uses TiO2 and Nb2O5 thin films. The precise measurement of the storage capacity of thin films as a function of thickness allows us to deconvolute bulk and interfacial contributions. We discuss the results in terms of bulk and space charge capacitance. The generalized treatment that comprises both contributions shows also how the ratio of both varies with the degree of storage. Meanwhile exploiting various techniques (bias dependent impedance, TEM and EELS) electric field and charge distributions from bulk to the interface region are investigated. In the same context we study the space charge behavior in a discretized manner rather than by using the analytical Poisson-Boltzmann function. In this way a more precise definition and demarcation of electrode and double layer capacity is achieved. In terms of application we expect this work to provide a better understanding of energy and power densities of storage devices which becomes particularly important for nanoionic systems.
Operando Measurement of Lithiation Gradients in NMC111-Argyrodite All-Solid-State Composite Cathodes
Authors: Stavola Alyssa M. , Guida Dominick P. , Bruck Andrea M. , Sun Xiao , Zhu Hongli , Gallaway Joshua W. 
Published: September 2023

Achieving the high energy density targets in all-solid-state batteries (ASSBs) will require thick cathodes optimized for full utilization of active material. In composite cathodes with sulfide SSEs, the exclusion of carbon additives makes cathode design to balance ionic and electronic conductivities all the more important. Li-Ni1/3Mn1/3Co1/3O2 (NMC111) is a widely studied cathode material for its high energy density and high working voltage. The lattice parameters of this well-studied structure directly correlate to the amount of Li in the material, allowing for very accurate measurements of lithium-ion concentration gradients (lithiation gradients) throughout the cathode depth.
Spatially resolved lithiation gradients in thick NMC111/ Li6PS5Cl composite cathodes were measured using operando energy dispersive X-ray diffraction (EDXRD) on sealed and pressurized ASSBs with varying relative amounts of cathode active mass (CAM) and SSE. Electrochemical impedance spectroscopy (EIS) and transmission line modeling were employed to test the ionic and electronic conductivities of composite cathodes with similar varied CAM and SSE ratios. The balance of ionic and electronic conductivities was found to influence not only the lithiation gradients and utilization of active material in the cell, but also the NMC structural change throughout the depth of the cell resulting in peak bifurcation in the NMC (003) diffraction pattern.
Sulfide ASSBs suffer from a large capacity loss on the first cycle due to formation of the cathode electrolyte interface (CEI). To study this interface formation and capacity loss, in situ EIS was performed during the first charge and discharge of the full cell (Li/In| Li6PS5Cl| NMC111/Li6PS5Cl). This piecewise EIS allows us to analyze both time dependent and state-of-charge dependent interfacial processes while the battery cycles with no modifications to cell design.

Acknowledgments

We acknowledge financial support from the National Science Foundation under Award Number CBET-ES- 1924534. This research used resources of the Advanced Photon Source beamline 6-BM, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.
Operando Quantification and Visualisation of Dendrite-Induced Stresses in Ceramic Electrolytes Via Photoelasticity
Authors: Athanasiou Christos E. , Fincher Cole D. , Gilgenbach Colin , Carter W. Craig , Chiang Yet-Ming , Gao Huajian , Sheldon Brian W. 
Published: September 2023

The measurement of stress fields around lithium metal dendrites in solid electrolytes in operating conditions is critical for the design of next-generation, dendrite-resistant solid electrolytes. Prior work, both experimental and theoretical, indicates that the developed stresses in the in the electrolyte can be significantly high. However, direct stress measurements are still missing as they entail inherent experimental difficulties associated with probing stress fields at small scale brittle specimens operando.
By employing the principle of photoelasticity combined with electrochemical cycling in a plan-view cell the aforementioned challenges are bypassed, allowing not only to track the stress field as the dendrite events progress, but also to obtain whole-field stress information on a propagating dendrite in an LLZTO electrolyte. This new experimental methodology allows for direct stress measurements around the dendrite tip. The experimental data demonstrate that the dendritic events at such current densities can be understood by the classic Griffith - Irwin fracture theory.
Operando X-Ray CT Analysis of Composite Electrode in All-Solid-State Battery Using Silicon Anode
Authors: Orikasa Yuki , Matsumoto Mao , Watanabe Ayaka , Sakka Yuya , Zhong Chengchao , Yamashige Hisao 
Published: September 2023

As a next-generation rechargeable battery, all-solid-state battery is expected for used in practical applications, in which electrolyte solution of the current lithium-ion battery is replaced with a solid electrolyte. To further increase the capacity of all-solid-state batteries, silicon is used as the anode active material forming an alloy with lithium. However, in the charge and discharge reaction using silicon anode, poor cycle capability due to the volume change of the silicon alloying reaction has been known. Many reports are limited to the analysis of the volume change of the whole electrode, and there are few reports on the quantitative analysis of the volume change of the silicon active material itself. In this study, X-ray computed tomography (X-ray CT) was used to analyze the expansion and contraction of silicon-active materials in all-solid-state battery. X-ray CT analysis can provide the contacted state information between electrode active materials and solid electrolytes [1]. By operando X-ray CT analysis, the expansion and contraction behavior of silicon particles during charging and discharging on the electrode was studied.
Nb-coated LiNi1/3Co1/3Mn1/3O2(NCM), Li10GeP2S12(LGPS), acetylene black (AB) mixed at a weight ratio of 1:1:0.2 were used as the cathode composite. Silicon, LGPS, AB mixed at a weight ratio of 1:1:0.1 were used as the anode composite. All-solid-state battery, Si | LGPS | NCM was assembled in a cylinder with an inner diameter 1 mm. The cell was brought into SPring-8 BL20XU beamline, and the operando X-ray CT measurement was carried out. From the obtained X-ray CT images, the three-dimensional analysis of silicon particles was performed.
Mean expansion coefficients of silicon‐particles traced during charging and discharging were calculated. The expansion of silicon particles by charging (lithiation) and the contraction of silicon particles by discharging (delithiation) are confirmed. Furthermore, the volume expansion rate of the silicon particles after the charging is average exceeded 300%. After discharge, silicon shrinkage is observed with delithiation, but the solid electrolyte cannot follow the volume change, and the silicon/solid electrolyte interface is broken. However, the contact is not completely failed, maintaining the partial contact between silicon and the electrolyte.
[1] Y. Sakka, H. Yamashige, A. Watanabe, A. Takeuchi, M. Uesugi, K. Uesugi and Y. Orikasa, J. Mater. Chem. A, 10 16602–16609 (2022).
Acknowledgement: This work was partially supported by the New Energy and Industrial Technology Development Organization (NEDO), JPNP20004.
The Zircon Structure As a Prototype Host for Fast Monovalent and Di-Valent Ionic Conduction
Authors: Chen Qian , Sari Dogancan , Rutt Ann , Kim Jiyoon , Ceder Gerbrand , Persson Kristin A. 
Published: September 2023

"Beyond Li-ion" energy storage solutions based on ions such as Na, Mg, Ca and Zn-ion have attracted increasing attention due to growing concerns about the cost, resource availability and safety of the currently dominant Li-ion batteries. One of the greatest challenges for beyond-Li systems, especially multivalent ones, is the lack of materials with high ionic mobility.
In this study, we find that zircon-type framework presents a unique structural environment that enables superior conduction of multiple species including Na+, Ca2+, Mg2+ and Zn2+, even in the dilute carrier concentration regime. Nudged elastic band (NEB) calculations show very low diffusion barriers for Na/Ca/Mg/Zn in pristine YPO4 and ab initio molecular dynamics (AIMD) simulations confirm the 1D percolating diffusion channel in the zircon-type framework. These 1D percolating channels of adjacent, distorted octahedral sites result in a smoothly varying coordination environment thus correspondingly low activation barriers. The phase stability of doped compositions is examined when both carrier ion and subvalent dopants are introduced into the system and confirm good stability through low decomposition energy of compositions with different carrier-dopant combinations. Among these compositions, we found Na0.0625YSi0.0625P0.9375O4 exhibiting a high Na+ conductivity of 0.99 mS/cm at 300 K with an activation energy of 220 meV. Finally, we identify dopant-carrier association in doped YPO4 as a key challenge for long-range diffusion in this structure family.
Macroporous Carbon Films Support Vs. Conventional Carbon Particles with FeN4 Sites for Oxygen Reduction in Gas-Diffusion-Electrodes
Authors: Kellner Simon , WANG Mengnan , Heutz Sandrine , Stephens Ifan E L , Titirici Magda 
Published: September 2023

Novel synthetic approaches have been developed to maximize the active site density of atomically dispersed Fe sites coordinated to nitrogen in carbon matrix. (Fe-N-C) (1,2) Nevertheless, the realistic maximum for single iron sites in these catalysts is deduced to be limited to 1021 sites per gram. (3) Therefore, for the application these Fe-N-C catalysts at the cathode for the oxygen reduction reaction in fuel cells, the catalyst material loading has to be increased to be able compete with the performance of Pt/C catalysts. Due to the resulting increased thickness of Fe-N-C catalyst layers, the oxygen available for the ORR at high current densities is dependent on the insufficient transport of oxygen across the catalyst layer. Freestanding catalyst nanostructured films, whose porosity is controlled across the entire thickness of the catalyst layer are expected to improve the mass transport at high current densities. Carbon nanostructures could provide the support substrate for such freestanding catalyst films. For instance, mesophase pitch-based films have been templated by silica (SiO2) nanoparticles have favourable morphologies for supporting Pt. (4) However, harsh conditions and long reaction times are required to etch away the SiO2. In our work, SiO2 nanoparticles are substituted by polystyrene nanoparticles, which decompose and tracelessly evaporate during the carbonization process. We have fabricated carbonized films of multiple thicknesses. We found 100 µm to be optimal, substantially thicker than Pt based electrodes to accommodate the lower density of sites and cheaper catalyst material. which is a usual thickness for Fe-N-C-based cathodes. Iron phthalocyanine (FePc) as a model active site is adsorbed on the freestanding carbon film. Gas-Diffusion-Electrodes (GDE) enable us to investigate the performance of such freestanding thin film catalysts at high current densities relevant for fuel cells. (5) A comparison of the ORR performance of catalyst layers, based on carbon films support (A) and conventional carbon particle support (B) are presented. We discuss the effect of adjusting the thickness of the two types of catalyst layers on the performance.
1 Barrio J, Pedersen A, Feng J, Sarma S. C., Wang M, Li A. Y. , Luo, H. Ryan M. P., Titirici M.-M., Stephens I. E. L. J. Mater. Chem. A, 2022;10: 6023-30
2 Mehmood A, Pampel J, Ali G, Ha H Y, Ruiz-Zepeda F, Fellinger T P Adv. Energy Mater., 2018; 8: 11649-55
3 Mehmood A, Gong M, Jaouen F, Roy A, Zitolo A, Khan A, Sougrati M.-T., Primbs M., Martinez Bonastre A, Fongalland D, Drazic G, Strasser P, Kucernak A Nat. Cat., 2022;5, 311-23
4 Atwa M, Li X, Wang Z, Dull S, Xu S, Tong X, Tang R, Nishihara H, Prinz F, Birss V 2021;8: 2451-62
5 Inaba M, Jesen A W, Sievers G W, Escudero-Escribano M, Zana A, Arenz M Energy Environ. Sci,2018;11: 988-94
Nanoelectrical Mapping of Carbon Nanofibers By Means of Peakforce Tunneling Atomic Force Microscopy
Authors: Borowec Julian , Selmert Victor , Kretzschmar Ansgar , Fries Kai , Tempel Hermann , Hausen Florian 
Published: September 2023

Electrospun polyacrylonitril (PAN) based carbon nanofibers (CNFs) are promising candidates for applications in energy conversion and storage. This originates from their electrical properties,[1] and their relatively easy manufacturing from abundant and cheap material.[2] However, the utilization of PAN CNF mats in devices such as electrolyzers is currently limited by their low conductivities. Advanced nanoelectrical characterization methods, such as Conductive Atomic Force Microscopy (C-AFM),[3] give insights into nanoscale limitations of the CNF’s conductivity. Revealing the limitations will help tailoring CNF’s conductivity. Thereby, a rational CNF design for applications in energy devices will be enabled.
In this work, morphology, structure and nanoelectrical properties of electrospun PAN CNF mats, which were carbonized at different temperatures, are investigated by means of PeakForce Tunneling Atomic Force Microscopy (PF TUNA, Bruker). Next to the fundamentals of PF TUNA, topography and current maps of PAN CNF networks are presented and critically discussed. Topography maps reveal relatively homogeneous CNFs, which are in line with the homogeneous currents detected across the CNF network. The detected current signals indicate electrically well-interconnected fibers within the mats. Consequently, poor fiber interconnections or heterogeneities are not the limiting factor for an ideal macroscopic conductivity. High resolution maps of CNFs show that a large fraction of the surface area is non-conductive and that the fraction of conductive domains depends critically on the carbonization temperature. The nanoelectrical currents detected by PF TUNA on CNFs carbonized at different temperatures correlate strongly to the respective macroscopic conductivities measured by the four point method.
The obtained results show that PF Tuna is a powerful tool to correlate nano- and macroscale conductivities. Future investigations, especially with CNFs containing integrated additives, will provide significant insights into nano- and macroscale relations and pave the way towards CNFs with desired electrical properties.
Literature:
[1] Gehring et al., RSC Adv. 2019, 9 (47), 27231–27241.
[2] Kretzschmar et al., ChemSusChem 2020, 13 (12), 3180–3191.
[3] Butnoi et al., JMR&T 2021, 12, 2153–2167.