Symposium CJ
Materials Demands Towards Next Generation Electrochemical Energy Storage Systems
ABSTRACTS
CJ-1:IL02 Sustainability Implications of Emerging Batteries – Prospective LCA of Sodium and Magnesium Batteries
M. Weil, J. Peters, C. Tomasini Montenegro, M. Baumann, KIT-HIU, KIT-ITAS, Karlsruhe, Germany
Lithium-Ion batteries (LIBs) can be considered as the state of art for electrochemical energy storage. In many mobile (e.g. electronics, electric vehicles –EVs-) and stationary applications LIBs dominates the market at present. But present LIB technology also has some drawbacks, which hinders e.g. the fast market breakthrough of EVs. The restricted availability (including environmental and social impact) of some raw materials like Cobalt, Nickel, Lithium and natural Graphite is a major obstacle. But also the high production costs, the limited life time (cycle lifetime, calendric lifetime), and costly recycling process are big issues. The group of Post Lithium Batteries (PLBs) are considered as an emerging technology to overcome the problems and limitations of LIBs, also if they are still far away from a technical application. In a prospective manner, the environmental impacts related to the manufacturing of a Magnesium and Sodium battery is analyzed, to identify the environmental hotspots within the production chain. This kind of information can be played back to the technology developers to improve the sustainability of such systems in an iterative manner in the further development process.
CJ-1:IL03 Operando Interface Characterization of Battery Materials
E.J. Berg, Department of Chemistry, Uppsala University, Sweden
Prolonging the Li-ion cell lifetime is necessary to reduce cost and environmental impact of battery ownership. A significant part of the problem, but also its solution, is the solid electrolyte interphase (SEI) on the negative electrode. Although required for a functioning cell, the SEI also consumes lithium/charge and adds a Li+ diffusion resistance, which increases upon cycling. Understanding the mechanisms behind specific charge loss and electrode impedance is crucial for improved battery cells. Operando characterization methods are preferred considering the complex dynamics of the SEI formation process, the nm-sized dimension of this interphase, as well as the intermediacy and instability of many interphase species. Operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCMD) coupled with Online Electrochemical Mass Spectrometry (OEMS) will be presented and shown to provide insights into the compositional, mechanical and electrochemical properties of the SEI. Critical constituents of an effective SEI will be discussed.
CJ-1:IL05 On the Road to a Multi-coaxial-cable Battery: Development of a Novel 3D-printed Composite Solid Electrolyte
D. Golodnitsky1,2, H. Ragones1, A. Vinegrad1, G. Ardel1, E. MADOS1, Y. Kamir1, M. Goor1, M.M. Dorfman1, A. Gladkikh2, 1School of Chemistry, Tel Aviv University, Tel Aviv, Israel; 2Wolfson Applied Materials Research Center, Tel Aviv, Israel
Several attempts have been made to produce primary and secondary thin‐film batteries utilizing printing techniques. These technologies are still at an early stage, and most currently-printed batteries exploit printed electrodes sandwiching self‐standing commercial polymer membranes, produced by conventional extrusion or papermaking techniques, followed by soaking in non-aqueous liquid electrolytes. In this work, we suggest a novel flexible-battery design and report the initial results of development and characterization of novel 3D printed all-solid-state electrolytes prepared by fused-filament fabrication (FFF). The electrolytes are composed of LiTFSI, PEO and PLA, which not only improves the mechanical properties of PEO, but also serves as a Li-ion-conducting medium. The flexible all-solid LiTFSI-based electrolyte exhibited bulk ionic conductivity of 3×10−5 S/cm at 90oC and 156 ohm/cm2 resistance of the solid electrolyte interphase (SEI). The feasibility tests of all-printed solid battery will be presented. These results pave the way for a fully printed solid battery, which enables free-form-factor flexible geometries.
CJ-1:IL06 Synthesis of Micron-sized Ni-Rich Li(Ni,Co,Mn)O2 and Assessment of Bimodal Distributed Li-ion Battery Cathodes
NAE-LIH WU, Chia-Hsin Lin, Wei-Hsiang Chen, Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan
The demand for Lithium-ion batteries (LIBs) with high energy density become indispensable owing to the widespread of electrification, especially for the electric vehicle applications. For the development of cathodes in LIBs, Ni-rich Li(Ni,Co,Mn)O2 cathodes, also known as the NCM cathodes, have been considered as promising candidates since the superior discharge capacity and operating voltage that result in high energy. The state-of-the-art commercial NCM materials are typically produced via a hydroxide-based precipitation process and composed of secondary particles of 10~15 microns in size. In this presentation, Ni-rich NCM powders of a few microns are produced using a facile oxalate precipitation process, and the LIB electrodes composed of bimodal distributed Ni-rich NCM particles are evaluated. The smaller NCM particles are situated within the voids between the larger NCM particle, leading to enhanced volumetric energy density. Interestingly, synergistic effects enabling substantially enhancements in both cycling and rate performances are also reported.
CJ-1:IL08 New Hydrides and Halides as Solid Electrolytes for Metal Ion Batteries
D.H. GREGORY, School of Chemistry, University of Glasgow, Glasgow, UK
Many of the most ubiquitous materials in Li-ion batteries are oxides. Nevertheless, some of the best performing materials contain elements from elsewhere in the periodic table (e.g. chalcogenides, pnictides). Although halide salts have long been employed as electrolytes in solution or in the molten state, there are few examples of halides as solid-state ionic conductors and until recently, still less in terms of hydrides. This contribution focuses principally on the possibilities for designing fast Li-ion conducting (pseudo-)halides as potential solid state electrolytes. In switching the materials design emphasis from cations to anions, it will be shown how both static and dynamic disorder might be exploited to enhance Li-ion transport and how diffusion pathways might be modified in terms of anion geometry and electronegativity. Synthesis can be challenging, but mechanochemistry and other “soft” chemical approaches, can provide a means to access such materials, while facilitating nanostructuring and generating defects. This contribution covers several exemplar systems of promising hydride and halide Li fast-ion conductors.
CJ-1:IL11 How do We Address Safety of Li-ion Battery and Na-ion Battery?
P. BALAYA, Department of Mechanical Engineering, Faculty of Engineering, National University of Singapore, Singapore
Li-ion battery technology has been widely accepted for electric vehicles and stationary storage applications to mitigate challenges due to climate change. In this context, several Li-ion battery chemistries have been successfully commercialized including LiFePO4/graphite (LFP), LiNi0.8Co0.15Al0.05O2/graphite (NCA), LiNi0.6Mn0.2Co0.2O2/ graphite (NMC) etc., Despite enormous efforts made on Li-ion cells of oxide chemistry most of the industries prefer using LFP chemistry in view of the excellent safety features despite its low energy density. In this presentation, we analyze various causes for improved safety of LFP cells. Impedance spectroscopy data analyzed suggest that the charge transfer resistance at the positive electrode is the major contribution to internal resistance and excess heat generation in the oxide-based Li-ion cells. The storage performances of a few selected 18650 type Na-ion cells will be presented. Analogous to Li-ion cells, it will be shown that the charge transfer resistance in the positive electrodes contributes largely to heat generation of such Na-ion cells. Various strategies will be discussed to minimize heat generation and the associate total internal resistances these Li-ion and Na-ion cell chemistries for improving their safety features.
CJ-1:L13 Formulating Stable Electrolytes for the Metal Anode in Alkali Metal-Oxygen Batteries
A.R. NEALE, Chih-Han Yen, L.J. Hardwick, Stephenson Institute for Renewable Energy, University of Liverpool, Liverpool, UK; R. Sharpe, Stephen R. Yeandel, P. Goddard, K.V. Luzyanin, Department of Chemistry, Loughborough University, Loughborough, UK; E.A. Petrucco, J. Matthey, Blounts Court Road, Sonning Common, Reading, UK
The realisation of a rechargeable metal-oxygen (M-O2) cell, capable of approaching the high theoretical specific energies (e.g. 3500 Wh·kg-1 for Li-O2), is hampered by material/intermediate instabilities that inhibit cell reversibility, efficiency and cycle life. Strategies to promote lower energy pathways to avoid large overpotentials are vital, as well as the design of new electrode and electrolyte materials to enhance stability in the reactive interfacial regions of both electrodes of the M-O2 cell. In this talk we present a formulation strategy, initially explored in Li-O¬2 systems, to dramatically enhance the stability of practically-relevant electrolyte materials that otherwise fail rapidly at the alkali metal anode. Consequently, improved cell cycle lifetimes are demonstrated and, using Raman spectroscopy and diffusional analyses, we relate this closely to the critical solvation environments involving the reactive component in optimised formulations. By understanding key shifts in Raman spectra relating to solvation effects in concentrated Li formulations, we further demonstrate the applicability of this relationship and formulation strategy to Na-O2 chemistries, wherein the more reactive Na anode presents greater stability challenges.
CJ-1:IL14 Insight into the Reactivity and Potential Profile across the Electrified Interface in All-Solid-State Batteries Enabled by Operando X-Ray Photoelectron/Absorption Spectroscopy
X. Wu, L. Höltschi, M. Mirolo, C.A.F. Vaz, C. Borca, T. Huthwelker, P. Novák, M. El Kazzi, Paul Scherrer Institute, Villigen PSI, Switzerland
All-solid-state batteries (ASSBs) are a rising alternative for boosting the volumetric energy density and promising a superior safety. However, ion transport across the solid electrolyte (SE)/active materials (AMs) interfaces is limited by poor mechanical contact and parasitic (electro-)chemical side reactions. The fundamental understanding of such interface has not been fully achieved yet mainly due to the limitations in current surface-sensitive analytical techniques, especially in operando mode. In this contribution, we will review the recent developments in operando X-ray photoelectron (XPS) and absorption (XAS) spectroscopy, to monitor in real-time the interface evolution of operational ASSB working electrodes. Operando measurements are made possible thanks to the unique and versatile electrochemical custom-made cell designed to operate in ultra-high vacuum, providing reliable electrochemistry. We will highlight how the combination of in-house operando XPS and synchrotron-based operando XAS using soft and tender X-rays can provide a reliable platform to investigate the (i) (electro-)chemical evolution of the SE/AMs interfaces, (ii) surface modifications of the AMs and (iii) electronic properties across electrified solid-solid interfaces.
CJ-1:IL16 Molecular-level Understanding & Design of Positive Electrode Materials For Rechargeable Aluminum Batteries
R.J. Messinger, The City College of New York, New York, NY, USA
Rechargeable aluminum (Al) metal batteries are an emerging energy storage technology with great promise: Al has among the highest capacities of common metal electrodes and is low cost, earth abundant, environmentally friendly, and inherently safe. Despite these opportunities, technological development of Al batteries has been hindered due to challenges associated with Al electrochemistry. Few electrolytes enable the reversible electrodeposition of Al metal at room temperature, while few positive electrode materials have been demonstrated that exhibit high energy density and cycle life in those electrolytes. Here, I will discuss recent progress in the molecular-level understanding and design of positive electrode materials for rechargeable Al batteries, including graphites, transition metal chalcogenides, elemental chalcogenides, and organic structures. Molecular-scale understanding of their charge storage mechanisms will be discussed, which vary greatly among the materials, as revealed by a combination of electrochemical, spectroscopic, diffraction, and computational methods, particularly solid-state nuclear magnetic resonance (NMR) spectroscopy. The results yield insights and design principles aimed at developing new electrode materials for rechargeable Al metal batteries.
CJ-1:IL22 In Situ Exploration of In-pore Redox Processes for Beyond Intercalation-type Energy Storage
C. PREHAL, S. Freunberger, V. Wood, Department of Information Technology and Electrical Engineering, ETH Zürich, Zürich, Switzerland; IST Austria (Institute of Science and Technology Austria), Klosterneuburg, Austria; Department of Information Technology and Electrical Engineering, ETH Zürich, Zürich, Switzerland
Properties and functions of beyond intercalation-type batteries are not only rooted in the chemistry but at least as much in the structure from atomic to sub-micrometer length scales. This applies specifically to lithium-sulfur (Li-S) or lithium-air (Li-O2) battery electrodes with complex transformations such as the electrodeposition and stripping of insulating materials. Identifying the critical structure-property relationships and physical-chemical mechanisms puts high demands on (in situ) experimental techniques. Here we present in situ small-angle x-ray and neutron scattering (SAXS / SANS) as suitable methods to study the nanoscale phase evolution of solid reaction products during device operation. Combined with stochastic modeling, we quantify the solid phase evolution in Li-S battery cathodes [1], Li-O2 battery cathodes [2], and aqueous Na-I based hybrid supercapacitor electrodes [3], at length scales hardly accessible to other methods. Results overturn parts of the currently accepted reaction mechanisms and provide guidelines for improved device performance.
References: [1] C. Prehal et al. Pre-print: https://doi.org/10.21203/rs.3.rs-818607/v1 [2] C. Prehal et al. PNAS 118, e2021893118, (2021) [3] C. Prehal et al. Nature Communications 11, 4838, (2020)
CJ-1:IL24 Aqueous Electrolytes for Aluminum Ion Batteries: Investigating Ion Transport and Association Effects by Multinuclear NMR
A. Zheng1, 2, G. Pastel3, M. Garaga1, M. Ding3, M. Schroeder3, K. Xu3, S. Greenbaum1, 2, 1Department of Physics & Astronomy, Hunter College of the City University of New York, New York, NY, USA; 2Graduate Center of the City University of New York, New York, NY, USA; 3U.S. Army Research Laboratory, Adelphi, MD, USA
Among the candidates competing with lithium ion battery technology for large-scale energy storage applications are aluminum-based systems, which have significant cost and safely advantages. In this work, we investigate aqueous electrolytes containing aluminum trifluoromethanesulfonate (AlTf3) ranging in concentration from 0.1m to 3.6m. Cation, anion, and water molecular self-diffusion coefficients were determined by pulsed field gradient nuclear magnetic resonance (NMR) measurements of the 27Al, 19F, and 1H nuclei, respectively. A special high-gradient probe was used for the 27Al measurements due to short relaxation times associated with nuclear quadrupole interactions characteristic of this spin-5/2 nucleus. The NMR results yield information on the degree of salt dissociation and Al ion transference at all concentrations. In particular, concentration-dependent 27Al chemical shifts are sensitive to local ion clustering evolution whereas 1H chemical shifts and lineshape analysis allow an estimate the ratio of free to bound water. Further, comparison of the calculated conductivity, via the Nernst-Einstein equation and NMR-determined ion diffusivities, with measured conductivity yields effective “free” ion concentrations, which may include protons in these acidic electrolytes.
CJ-1:IL25 Cross-talk Suppressing Multifunctional Electrolyte Additives for Enhanced Interfacial Stability of Ni-rich NCMs
S. TRABESINGER, Battery Electrodes and Cells Laboratory of Electro-chemistry, Paul Scherrer Institute, Villigen PSI, Switzerland
The energy density of Li-ion batteries can be increased either by raising the specific capacity or cell voltage, and in pursuit of this goal, more research efforts are dedicated to develop cathode materials with high specific capacities, operating at high voltages. The Ni-rich layered oxides (LiNixMnyCozO2; x≥0.6, x+y+z=1, Ni-rich NCMs) have a high practical specific capacity (180 mAh g−1 with the upper cutoff potential of 4.2 V vs. Li+/Li), however, even higher capacity can be reached by Ni-rich NCM cathodes if the voltage window would be extended to potentials above 4.2 V, even if the voltage window is increased only by 0.1 V. However, both limited anodic stability of the standard electrolytes above 4.2 V and instability of Ni-rich NCM cathode materials interface in a highly-charged state make high-voltage performance difficult to achieve. In this talk, two multifunctional additives will be presented, mitigating the cycling stability issues of graphite‖NCM851005 cell as a whole, as well as for preservation of graphite and Ni-rich layered oxide materials structures individually, even with high upper cutoff voltage up to 4.35 V (4.4 V vs Li+/Li). As well teh importance of the full-cell testing for additive compatibility will be discussed.
CJ-1:IL26 Prospects for Industrial Scale Vanadium Redox Flow Batteries
M. GUARNIERI, Department of Industrial Engineering, University of Padua, Interdepartmental Centre Giorgio Levi Cases for Energy Economics and Technology, University of Padua, Padova, Italy
Energy storage is a key technology for the transition to decarbonized energy in smart grids, being able to provide different services, classified into energy management, with long discharges, and power quality, with fast responses. Recently, the interest for long storage is also emerging, e.g. in seasonal storage. Different technologies are available to store energy, among which closed batteries (lithium, sodium, …) are strong enablers, thanks to features such as low environmental impact, flexible location, scalability, stillness, high efficiency. However, closed batteries present issues e.g. life duration, safety and self-discharge. In this framework, redox flow batteries (RFB) bare emerging as a competitive option for several services. Storing energy in liquid electrolytes kept in tanks outside the reactor, they provide independent sizing of energy and power, thus allowing for long discharge times at full power which are inaccessible for closed batteries. Their most developed version, the vanadium RFB, exhibits very long life, virtually no self-discharge, operation at room temperature and pressure and absence of hazard risks such as fires and explosions. While these VRFBs are in an early market phase, more research is needed to improve their performance and competitiveness.
CJ-1:L27 Operando Optical Diagnostics of Battery Chemistries
L.J. Hardwick, Stephenson Institute for Renewable Energy, Department of Chemistry, University of Liverpool, UK
The performance and safety of batteries are affected by the side reactions and passivation layer at the electrode/electrolyte interface. Therefore, it is essential a better understanding of the reactions mechanisms that lead to surface layer formation and the chemistry within both lithium-ion and lithium-oxygen (Li-O2) batteries. Surface-enhanced Raman spectroscopy (SERS) is a powerful technique used in operando conditions to investigate electrode surface interactions under potential control during battery cycling. Since SERS has limitations in terms of substrate nature and morphology, shell isolated nanoparticle Raman spectroscopy (SHINERS) is an alternative technique for surface analysis. In this case Raman signal amplification comes from the gold core embedded in an ultrathin silica shell (SHINs) of the nanoparticles deposited on the electrode surface, and in principle any type of electrode substrate can be investigated. Within this presentation I will demonstrate how these Raman techniques can be used to investigate oxygen reduction reaction (ORR) mechanisms in metal-oxygen cells and introduce how complementary techniques, such as surface enhanced infrared spectroscopy, assist in understanding the particular chemical environment at the electrode/electrolyte interface.
CJ-2:IL06 Solution Processed Cu Oxide/Fe Oxide Electrode for Supercapacitor
h.-e. lIN1, m. UemURA1, y. KATAyANAGI2, y. KUBoTA1, N. MATSUSHITA1, R. NITTA1, 1Department of Materials Science and Engineering, Tokyo Institute of Technology, Tokyo, Japan; 2Department of Technology Education, Faculty of Education, Gunma University, Gunma, Japan
Supercapacitors (SCs) is recognized as a promising energy storage device, since it possesses several advantages such as fast charging/discharging traits, high power density, long cycle life and so on. The binary composite Cu2-xO-αFe2O3 films applicable as anodic material of supercapacitor were fabricated by spin-spray process on FTO glass substrate at substrate temperature of 90℃. Here, α-Fe2O3 (F-C0), CuO-αFe2O3 composite (FC-1) and Cu2O-αFe2O3 composite (FC-2) were prepared by controlling the precursory ion-molar-ratio of the source solution. Although the films of α-Fe2O3 (F-C0) surface exhibited an incomplete wetting trait toward water (θc>90˚), the surface of Cu2O-αFe2O3 composite (FC-2) exhibited the water contact angle lower than 10˚ with good wettability. The supercapacitor assembling with the FC-2 electrode exhibited area normalized capacitance of 182.4 mFcm-2 at 0.5 mAcm-2, which is approximately 150 times higher than that corresponding to the FC-0 electrode (1.2 mFcm-2 at 0.5 mAcm-2). It performed the capacitance retention of 92.5% suggesting a good long-term cycling stability. The spin-sprayed Cu2-xO-Fe2O3 composite film is a promising candidate for high performance electrode material of supercapacitor.