Symposium FE
Next Generation Electrochemical Energy Storage Materials and Systems
ABSTRACTS
Session FE-1 Batteries
FE-1:IL01 Stable Solid State Batteries through Interfacial Engineering
PING LIU, University of California, San Diego, La Jolla, CA, USA
Managing the behavior of numerous solid-solid interfaces is crucial in realizing long service life for solid state batteries. We have been developing numerous interfacial engineering strategies to address the various interfacial instabilities. On the anode side, we have studied how carbon composites can serve as effective interlayers and uncovered that lithium goes through a surface-mediated transport process when there is limited intercalation into the carbon material. We have also recently discovered an organic compound that can serve as an artificial solid electrolyte interface (SEI) which effectively mitigates the parasitic reactions and enable the formation of clean lithium layer. In the electrolyte layer, we have focused on minimizing residual voids during processing. Modifying the electrolyte surface with a long chain alkyl thiol can help lubricate the particles and promote the densification of the electrolytes. Such surface modification is also shown to be effective against moisture penetration, greatly enhancing the stability during processing.
FE-1:IL02 Superionic Composite Electrolytes with Perpendicularly-Aligned 2D Pathways for All-Solid-State Batteries
XUEXIA LAN, JING PENG, HUI-MING CHENG, Institute of Technology for Carbon Neutrality, Shenzhen Institutes of Advanced Technology, CAS, Shenzhen, China
Solid electrolytes are promising candidates for safe, high-energy power systems. Composite electrolytes, in particular, hold the potential to combine high ionic conductivity with stable electrode interfaces. However, a fundamental trade-off often exists between ion conduction and mechanical properties. We introduce a composite electrolyte design that decouples ion conduction from mechanical flexibility, achieving a high ionic conductivity of 10.2 mS cm-1 at room temperature while maintaining intimate electrode contact. The architecture features alternating layers of perpendicularly aligned Li0.3Cd0.85PS3 (PA-LiCdPS) to create continuous superionic conduction pathways and polyethylene oxide (PEO) for flexibility and improved interfacial compatibility. This PA-LiCdPS/PEO electrolyte enables Li||LiNi0.8Co0.1Mn0.1O2 coin cells (stack pressure <0.5 MPa) to retain 92% capacity after 600 cycles at 0.2 mA cm-2, with cycling Coulombic efficiencies of 99.9%, and also facilitates practical use of pressure-less (<0.1 MPa) pouch cells. This design strategy is further validated in the PA-Li0.46Mn0.77PS3/PEO electrolyte, achieving a room-temperature ionic conductivity of 6.1 mS cm-1 and mechanical flexibility. The elemental availability of Li0.46Mn0.77PS3 enhances its practical applicability.
FE-1:IL03 Electrochemical Charge Storage in MXenes
MASASHI OKUBO, Waseda University, Tokyo, Japan
All-solid-state batteries with non-flammable inorganic solid electrolytes are a key technology to address the safety issues of lithium-ion batteries with flammable organic liquid electrolytes. However, conventional electrode materials suffer from substantial volume change during lithium-ion (de)intercalation, leading to the failure of the interface between the electrode materials and solid electrolytes and then severe performance degradation. In this work, we report strain-free charge storage via an interface between a transition-metal carbide nanosheet (MXene) and solid electrolytes, where MXene shows negligible structural change during lithium-ion (de)intercalation. Combined assessment including operando STEM-EELS elemental mapping clarified the strain-free nature of the MXene electrodes in the all solid-state batteries. In addition, the irreversible reactions at the MXene-electrolyte interface is visualized, explaining the inital irreversible capacities and relatively low rate capability of the MXene electrodes. A strain-free all-solid-state battery, which consists of Ti3C2Tx anode and disordered rocksalt Li8/7Ti2/7V4/7O2 cathode, demonstrates a long-term operation owing to the strain-free nature of both electrode materials.
FE-1:IL04 High-Capacity Anode Materials for Solid-State Batteries
M.T. McDOWELL, G.W. Woodruff School of Mechanical Engineering, School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA, USA
Solid-state batteries offer the promise of improved energy density and safety compared to lithium-ion batteries, but chemo-mechanical evolution and degradation of materials and interfaces play an outsized role in limiting their performance. Here, I will discuss my group’s work on solid-state batteries with both lithium metal and alloy-based anodes. We show that introducing sodium into a lithium metal electrode to form a multi-phase lithium-sodium composite results in excellent cycling performance at low stack pressure. This is due to the mechanically soft sodium deforming and accumulating at the solid-state interface during lithium stripping. The electrical conductivity and deformability of sodium mitigate void formation and also allow for subsequent lithium deposition and cycling under low stack pressure. Furthermore, using sodium metal directly as a current collector also shows mechanistic benefits. Next, I will introduce our work on understanding the behavior of alloy anodes for solid-state batteries, including silicon, aluminum, and tin. We show that alloy metal anode morphology changes during charge/discharge are highly pressure dependent. Engineering the alloy interface with materials that remain dense during cycling enables better interfacial contact and improved long-term performance.
FE-1:IL05 Hybrid Materials as a New Lever for All-Solid-State Battery Performance
R. CHOMETON1,2,3, I. GHILESCU1,2,3, K. VAR1,3, B. SEGUY-BLONDEL1,3, A. PEREZ1,2,3, E. BARTHEL4, J.-M. TARASCON1,2,3, C. LABERTY-ROBERT1,3, 1Laboratoire de Chimie des Matériaux Inorganique, Sorbonne Université, Paris, France; 2CSE, Collège de France, Paris, France; 3Réseau sur le Stockage Electrochimique de l’Energie, RS2E, FR 3459, Amiens, France; 4ESPCI Paris, PSL University, Sorbonne Université, CNRS, Laboratoire Sciences et Ingénierie de la Matière Molle, Paris, France
All-solid-state batteries (ASSBs) have drawn significant interest from the electric vehicle industry due to their high energy density and potential enhanced safety. Given these promising characteristics, this emerging technology clearly stands out as a favored solution. However, while this technology is the focus of extensive research and considerable attention, its promises still need to be validated to determine if it truly represents a technological breakthrough. The primary technological challenges hindering the development of ASSBs are related to interface management and stability throughout the assembly and operational phases. For example, compositional variations within cathode particles create mechanical issues at the contact points between electrode particles (which expand or contract) and the solid electrolyte. On the anode side, lithium metal deposition induces "complex" stress at the interface with the solid electrolyte, leading to deposition not only at the electrode-electrolyte interface but also within the solid electrolyte itself, in its pores or along grain boundaries. Additionally, confined lithium deposition generates areas of high "hydrostatic" stress, causing fractures in the electrolyte. The integration of hybrid materials into these ASSBs offers an opportunity to address these challenges by improving the management of solid/solid interfaces during cycling. However, a significant challenge lies in the implementation of these hybrid materials, which often require multi-step fabrication processes that are poorly suited to large-scale production and carry a significant environmental footprint. After describing various assemblies of hybrid materials, we will examine the different approaches to manufacturing them. In particular, we will explore the links between performance and assembly. This includes addressing the question of conductive vs. non-conductive polymers in the context of electrolytes.
Targeting the Right Metrics for an Efficient Solvent-Free Formulation of PEO:LiTFSI:Li6PS5Cl Hybrid Solid Electrolyte, R. Chometon, M. Deschamps, R. Dugas, E. Quemin, B. Hennequart; M. Deschamps, J.M.T. Tarascon, C. Laberty-Robert, ACS Applied Materials and Interfaces,15, 50, 58794-58805, 2023.
Correlation between Ionic Conductivity and Mechanical Properties of Solid-like PEO-based Polymer Electrolyte, A Naboulsi, R Chometon, F Ribot, G Nguyen, O Fichet, C Laberty-Robert, ACS Appl. Mater. Interfaces, 16, 11, 13869–13881, 2024.
Characterization of Li+ Transport through the Organic-Inorganic Interface by Using Electrochemical Impedance Spectroscopy, A. Naboulsi, S. Franger, G. Nguyen, O. Fichet, C. Laberty-Robert, J. Electrochem. Soc. 171 020523, 2024.
Functional composite separators with cations trapping abilities, J. Richard, N. Solati, A. Singh, V. Meunier, Y. Toda, A. Grimaud, A. Perez, C. Laberty-Robert, ACS Applied Energy and Materials, accepted, april 2024.
FE-1:L06 Decoding the Solution-Mediated Formation of Sulfide Electrolytes for Next Generation Solid-State Batteries
A. PURGATORIO, L. ROCCHIGIANI, A. MACCHIONI, Department of Chemistry, Biology and Biotechnology, University of Perugia, Perugia, Italy; F. DUCALE, M. LEONARDI, Italmatch Chemicals S.p.A., Spoleto, PG, Italy; R. DUFRENE, C. MASQUELIER, Laboratoire de Réactivité et de Chimie des Solides, Université de Picardie Jules Verne, Amiens, France; L. TENSI, Department of Pharmaceutical Sciences, University of Perugia, Perugia, Italy
All-solid-state batteries represent a promising solution for safer and higher-performance energy storage systems. Sulfide-based electrolytes are particularly appealing due to their excellent ionic conductivity and mechanical compliance, although their performance strongly depends on the synthesis route. Among various strategies, solution-based approaches have recently gained attention as scalable alternatives, yet their underlying mechanisms remain poorly understood. This study investigates the reactivity between metal sulfides (MₓS, M = Li, Na, K, Ca) and P₄S₁₀ to elucidate the speciation processes occurring in solution. Combined spectroscopic and structural analyses reveal the transient formation of reactive intermediates, including a previously unreported P₄S₁₁²⁻ species, which subsequently evolves into diverse thiophosphate compounds that give rise to the desired solid electrolytes. These findings offer molecular-level insight into thiophosphate chemistry and establish a foundation for scalable, cation-independent synthesis routes toward next-generation sulfide electrolytes for all-solid-state batteries.
FE-1:L07 Hydride Ion Conduction and Hydride Ion Battery
PING CHEN, Dalian Institute of Chemical Physics
Hydride ion has unique characteristics, such as high polarizability and strong reducibility. Facile H migration in rare earth trihydrides (REHx) have been known for decades. However, REHx are mixed conductors having strong and adverse electronic conductivities (σe). Our recent research results show that by creating grain boundaries and defects in the lattice, the electronic conductivity of REHx can be depressed by more than 5 orders of magnitude. Specifically, LaH3 turns to a superionic state at -40 ℃ with a hydride ion conductivity > 1.0 × 10-2 S/cm and diffusion barrier < 0.15 eV.[1] Hydride ion-mediated electrochemical process is fundamentally different from existing systems and enables the development of innovative electrochemical devices, such as rechargeable batteries, fuel cells, and electrolytic cells. We constructed an all-solid-state rechargeable hydride ion battery CeH2|hydride ion conductor|NaAlH4, which operates at ambient conditions and has an initial specific capacity of 984 mAh g−1 and retains 402 mAh g−1 after 20 cycles.[2] Using hydrogen as charge carriers can avoid the formation of detrimental metal dendrites, in principle, which creates new research avenues for clean energy storage and conversion.
FE-1:L07b Solid Electrolytes for Sodium Ion Batteries: From Thiophosphates to Eutectogels
A. HARDY, M. SALEH, J. MERCKEN, D. DE SLOOVERE, Hasselt University, Institute for Materials Research, imo-imomec, DESINe group, Diepenbeek, Belgium
Sodium ion batteries are gaining attention due to their sustainability potential, improved cost-effectiveness, and low T performance compared to LIB. Solid electrolytes for SIBs could possibly improve safety, avoid leakage, and increase energy density. Two different families of solid electrolytes will be discussed: thiophosphates, besides iono- and eutectogels. For the Na3PS4 solid electrolytes, the reasons for the lower conductivity of liquid phase synthesized materials as compared to those from ball mill methods will be discussed. Next, the effect of selenium doping as a means of enhancing the conductivity of the liquid phase synthesized material will be shown, as well as its application in all solid-state sodium batteries¹. For the silica-based ionogel electrolytes, it was found that organic modification of the silica backbone will improve the mechanical properties, at the cost of lower conductivity (2). Understanding the underlying reasons for this decrease at the atomic level, led to a eutectogel electrolyte, containing a DES instead of a ionic liquid (3).
1. M. Saleh et al. Physica Status Solidi:A 2025 accepted; 2. J. Mercken et al. ChemSusChem 2025 18 (14) e202500427; 3. A.-S Kelchtermans et al. ACS Omega 2024 9 (41) 42343–42352.
FE-1:IL08 Novel Hard Carbon Materials for High-capacity Li-ion Storage
CHI-CHANG HU, LIANG-CHIEH TSENG, CHEN-WEI TAI, YUN LIN, National Tsing Hua University, Hsinchu, Taiwan
Hard carbon (HC) has achieved huge success in sodium-ion batteries (SIBs) with a plateau capacity in the low-potential regime extending the working voltage of full cells, similar to graphite in lithium-ion batteries (LIBs). However, this unique electrochemical signature is rarely observed in the application of HC in LIBs, due to the inherent differences in the HC microstructure and Li⁺ storage mechanism at the low-potential regime. Herein, PF resins with controllable cross-linking density (CLD) is used to fabricate HCs. The microstructures of oligomers are carefully controlled. Contemporary material analyses reveal that low-CLD precursors tend to form pseudo-graphitic layers at early stage, generating abundant closed pores under suitable carbonization condition. A good correlation between Li-ion plateau capacity and closed pore volume along with in-situ XRD and Raman analyses confirms that low-potential plateau results from Li+ filling into closed pores in these novolak-derived HCs. Consequently, the HC with optimal synthesis conditions achieves a reversible capacity of 550 mAh g⁻1, including nearly 50% plateau capacity (255 mAh g⁻1). This work provides comprehensive understanding in closed pore engineering for high-capacity Li-ion storage.
FE-1:IL09 Recent Progress with Polymer-based Electrolytes for Rechargeable Batteries
D. BRESSER, Helmholtz Institute Ulm (HIU), Ulm, Germany; Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany; Ulm University (UUlm), Ulm, Germany
Polymer electrolytes based on poly(ethylene oxide) have been successfully commercialized in lithium-metal batteries. However, the rather low ionic conductivity at room temperature results in the need for a continuous heating of the battery cell to about 60-80 °C upon operation and also when charging the battery. This low ionic conductivity in combination with the rather limited electrochemical stability towards oxidation restricts the choice of active materials for the positive electrode to those with a de-/lithiation potential well below 4 V. Herein, a comprehensive overview of our activities to overcome these challenges will be provided, including the (partial) decoupling of the charge transport from the polymer dynamics, thus achieving substantially higher ionic conductivities, and the careful design of the polymer architecture in order to increase the electrochemical stability towards oxidation, while simultaneously maintaining suitable mechanical properties, high safety, and the compatibility with lithium metal at the negative electrode. The work is dedicated to the development of a fundamental understanding of the relevant impact factors that enable the realization of high-performance polymer-based electrolyte systems for high-energy lithium-metal batteries and beyond.
FE-1:L10 CVD Polymers for Artificial SEI Design in Batteries
SUNGHWAN LEE, YUXUAN ZHANG, YEONGJUN OH, School of Engineering Technology, Purdue University, West Lafayette, IN, USA
This presentation introduces a vapor-phase chemical vapor deposition (CVD) polymer strategy as an electrode and interphase modifier for advanced battery systems. The conformal CVD polymer coating enhances electronic conductivity by forming a continuous conductive network, buffers volume changes during cycling, and eliminates the need for conventional binders (e.g., PVDF) due to its intrinsic adhesion. The ultrathin, uniform layer also shortens ion diffusion pathways and reduces interfacial resistance, facilitating efficient ion transport. This multifunctional modification enables ultra–high active material loading (~99 wt%) in Li-ion batteries and suppresses polysulfide shuttling in Li–S systems, as well as stabilizing the cathode–electrolyte interface both electrochemically and mechanically. Comprehensive structural and electrochemical analyses, complemented by density functional theory (DFT) calculations, reveal the atomic-scale mechanisms behind these enhancements. Overall, CVD polymer surface modification offers a versatile route toward practical, ultrathin interfacial engineering in next-generation batteries.
1. Zhang et al. Energy Storage Materials, 48, 1–11, 2022. 2. Zhang et al. Nano Energy, 115, 108756, 2023.
FE-1:L11 Synthesis of Oxy-thiophosphates Solid Electrolytes for Sodium All-Solid-State Batteries
R. DUFRENE, P. GIBOT, C. MASQUELIER, Laboratoire de Réactivité et de Chimie des Solides (LRCS), CNRS UMR 7314, Université de Picardie Jules Verne, Amiens, France; Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, France
In order to improve battery cost and safety, Sodium All-solid-state Batteries have recently attracted significant attention and, among solid electrolyte materials, the sodium tetrathiophosphate Na3PS4, possesses a high ionic conductivity of 2×10-4 S/cm at 25°C. Unfortunately, it’s also very reactive with metallic sodium and unstable against moisture. To address these stability issues, oxythiophosphate compositions (Na3PS4-xOx ; x=1, 2 or 3) are being studied, as the Na3PS3O phase was recently reported to be stable with respect to metallic sodium. This present work focuses on the synthesis of Na3PS3O phase by different methods, such as solution synthesis and mechanochemistry. Different precursors were investigated, like the Na3PS4/Na3PO4 binary or by mixing Na2S, P2S5 and P2O5. Amorphous and crystalline phases were thus prepared and deeply characterized through MAS NMR, Raman spectroscopy and XRD. Synthesis in the liquid medium allows PS3O units to form in greater proportions than with mechanochemistry. Indeed Ball-milling leads to a phase composed of a PS4 matrix with different PS4-xOx units and requires an annealing step to control PS3O formation. Generally speaking, crystallized phases present higher chemical stability, while amorphous ones exhibit higher ionic conductivity.
FE-1:IL12 Defect-engineered Lithium Insertion Materials for Practical Li-ion Battery Applications
NAOAKI YABUUCHI, YOSUKE UGATA, Yokohama National University, Yokohama, Japan
Ni-rich layered oxides such as LiNiO2 are attractive positive electrodes, but suffer from capacity degradation at high voltages due to Ni migration. Recent studies show that non-stoichiometry and antisite defects play a critical role, and defect engineering enables highly reversible pure Ni-based layered materials without metal substitution. In parallel, Co-/Ni-free Mn-based electrodes are important for cost-effective electric vehicles. While typically synthesized by energy-intensive milling, nanostructured LiMnO2 with high energy density (~800 Wh kg–1) has recently been obtained through conventional calcination, demonstrating scalability. For safety, solid electrolytes are promising, but electrode volume changes complicate interface stability. Dimensionally invariable cation-disordered rocksalt oxides address this issue, achieving excellent reversibility with solid electrolytes. Overall, defect-engineered and nanostructured lithium insertion materials are central to the development of safe, high-energy, and practical Li-ion batteries.
FE-1:L13 Nanoscale Interface Design Strategies for Realizing Anode-Free Lithium and Sodium Batteries
L. FALLARINO, A. RAFIQUE, A. PESCE, M. YALÇINOZ, P.P. LÓPEZ-ARANGUREN, R. CID, CIC energiGUNE, BRTA, Vitoria - Gasteiz, Spain
In the direction of preserving the exceptional energy density of alkali metal batteries, while overcoming their inherent drawbacks, the transition towards anode-free architecture is underway, by eliminating the metallic anode and relying on in situ metal plating.[1] Still, a central challenge is the uncontrolled nucleation and uneven growth of alkali metal deposits at the electrolyte–current collector interface. Tailoring this interface is therefore of prime importance to promote uniform metal plating/stripping and enhance cycling stability and safety. Herein, we demonstrate a nanoscale interface material design via sputtering technique, [2-4] exploring a wide parameter range and elemental composition. The modified interface promotes the in situ creation of alkaliphilic phases that support long-term plating/stripping processes. These findings demonstrate a simple and effective interfacial engineering strategy to enhance the performance of anode-free batteries, providing a pathway toward safer and long-lasting devices. [2-4]
[1] L. Fallarino et al. Adv. Energy Mater 2024, 13, 2203744. [2] L. Fallarino et al. Chem. Comm. 2023, 59, 12346-12349. [3] A. Rafique, L. Fallarino, et al. Chem. Eng. J. 2025, 509, 160956. [4] M. Yalçınöz, L. Fallarino, et al. JPhys Energy 2025, accepted.
FE-1:L14 Healable Binder for Positive Electrode in Lithium Batteries
A. BEDAIDIA, I. TRIFI, G.T.M. NGUYEN, O. FICHET, CY Cergy Paris Université, Cergy-Pontoise, France
Lithium-ion batteries are promising systems for mobile devices and electric vehicles. With the rapidly increasing demand for these systems, achieving stable and reliable long-term performance has become a critical challenge, requiring the establishment of a durable operating environment for both cathode and anode materials. Within this context, binders play a pivotal role in electrode fabrication by ensuring strong adhesion between active materials, conductive additives, and the current collector. Despite being electrochemically inactive, binders exert a significant influence on electrode performance. We present here the fabrication of an elastomeric healable binder for positive electrode. Thus, a covalent adaptable network is synthesized by crosslinking a commercial terpolymer of Poly(ethylene oxide-co-epichlorohydryl-co-allylglycidyl ether) using 2,2′-(1,4-Phenylene)-bis[4-mercaptan-1,3,2-dioxaborolane] as crosslinker. The latter contains exchangeable boronic ester bonds, conferring to the material self-healing capacity. NMC based positive electrodes are formulated incorporating the resulting binder via an in situ crosslinking reaction. Healing properties of the binder and those of resulting positive electrodes as well as their electrochemical properties will be discussed.
FE-1:L15 Macroporous Carbon-Based Additive Boosting the Long-Term Stability of Li-S Batteries
M. ZUKALOVA, T. SUPINKOVA, B. PITNA LASKOVA, L. KAVAN, J. Heyrovsky Institute of Physical Chemistry, CAS, Prague, Czech Republic
Li–S batteries represent a promising energy storage technology due to their high theoretical capacity, low cost, and environmental friendliness. However, their practical deployment remains limited by capacity fading during cycling, primarily caused by the “shuttle effect” associated with the reactivity of lithium polysulfides. Within the HE project ANGeLiC, the research aims to develop advanced Li–S batteries combining high energy density, cost-effective manufacturing, and superior functionality—surpassing current Li-ion technologies. In the initial phase, targeting the strategic objective “Design high-capacity Li–S cells integrating innovative materials,” monodisperse macroporous carbon cathodes were synthesized via glucose pyrolysis using silica spheres as a template. The resulting Li–S cell achieved an initial capacity exceeding 700 mAh/g of S with less than 10% capacity loss over 120 cycles at 0.1 C, demonstrating strong potential for high-performance energy storage applications.
This work was supported by the EU Horizon Europe project No. 101202842/ANGeLiC.
FE-1:L16 Soft-Confinement-Gated OHP/IHP for Ion-Capacitive Storage
XINYUAN LI, HONG JIN FAN, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore
Electrochemical energy storage demands devices that combine battery-level energy with capacitor-grade power. We will elucidate a soft-confinement–gated mechanism in aqueous Zn-ion capacitors that helps overcome this intrinsic trade-off. A Zn2+-assisted soft-confined carbon (SCC) series is synthesized to tailor 0.86–3 nm pores with ultrahigh surface area. Operando IR/Raman reveal two voltage windows in which sulfate forms inner-sphere adsorption (IHP), separated by a valley dominated by outer-Helmholtz-plane hydration (OHP). The Raman band at 1040 cm−1 appears–disappears–appears with voltage (symmetry-broken sulfate in IHP), while IR 3230 cm−1 (strongly H-bonded interfacial water) varies in phase and IR 1120 cm−1 (ν3 of SO42−) tracks coverage with reversible hydrogen-bond shifts. We show that water-activity–dominated regimes lower desolvation barrier and favor IHP, whereas dielectric-saturation–dominated regimes rebuild water bridges and stabilize OHP. EQCM quantifies potential-dependent co-transport of hydrated ions/solvent, and potential-resolved EIS during charge/discharge exposes pronounced hysteresis, linking interfacial solvation switching to polarization. These results connect pore-scale confinement and interfacial water structure to capacitance and rate, yielding design rules to widen IHP windows and suppress passivation in aqueous Zn-ion capacitors.
FE-1:IL17 A Review of Neutron Techniques to Characterize in-situ and Operando Energy Storage Materials as Li-ion and Na-ion Cells
R. GILLES, TU Munich (MLZ), FRM II, Garching, Germany
Non-destructive investigations for in-situ/operando studies of Li-ion or Na-ion batteries are challenging and enable significantly more detailed insights into the processes during charging/discharging and aging. A zoo of neutron methods is be applied to investigate unexplained phenomena in battery cells of various types on specific length or time scales, primarily in a non-destructive manner. Neutron diffraction (ND) can effectively track in situ the changes in a commercial 18650 NMC/Graphite round cell. Crystallographic structural changes are characterized e.g. in the NMC material and during the evolution of graphite to LiCx phases. Neutron radiography (NR) or neutron tomography (NT) are used to directly visualize the cells or the electrolyte filling process, allowing spatial inhomogeneities in battery cells/components down to <3x10-5 m to be directly observed. In addition, near-surface Li depth profiles with a resolution of up to 10–50 nm are measured using neutron depth profiling (NDP) to characterize the Li distribution/gradient in the near-surface layers. Diffusion processes over shorter and longer distances in the time range from ms to ps, which occur e.q. due to Na-ion hopping in a crystallographic structure, are measured using quasi-elastic neutron scattering (QENS).
FE-1:IL18 Crystal Chemistry of Important Polyanionic Materials used as Cathodes in Sodium-Ion Batteries: the decisive impact of Synchrotron X-Ray diffraction
C. MASQUELIER1, S. PARK1,3,4, M. BIANCHINI1,3, L. NGUYEN1,3, F. FAUTH2, D. CARLIER3, P. CANEPA5, J.N. CHOTARD1, L. CROGUENNEC3, 1LRCS, Université de Picardie Jules Verne, UMR CNRS 7314, Amiens, France; 2ALBA synchrotron, Spain; 3ICMCB, Université de Bordeaux, UMR CNRS 5026, Pessac, France; 4TIAMAT Energy, Amiens, France; 5University of Houston, USA
Polyanionic materials (phosphates in particular) are of special interest as positive electrodes for Li-Ion or Na-ion batteries since they offer competitive performances compared to sodiated or lithiated transition metal oxides. They are based upon stable frameworks which provide long-term structural stability thanks to a unique variety of atomic arrangements. The fluorinated vanado-phosphate Na3V2(PO4)2F3 possesses quite extraordinary features in terms of performances at very high rates and for extensive electrochemical cycling and is now developed by the company TIAMAT as their cathode material in commercialized batteries. Very early preliminary studies conducted in ALBA Synchrotron gave us the opportunity to determine ist real crystal structure and to reveal subtlle phase transformations upon Na+ extraction. The NASICON structural family, on the other hand, with its large panel of compositions, NaxMM’(PO4)3 (0 < x < 4 ; M,M’ = Ti, Fe, V, Cr, Mn) is among the most widely investigated due to its 3-D framework structure which generates high Na+ mobility. Among them Na3V2(PO4)3, Na4MnV(PO4)3 and Na4FeV(PO4)3 are of particular interest. We will present several new structures, from pristine powders or for intermediate compositions spotted by operando X-ray diffraction.
FE-1:L19 Characterization of Pulsed Laser Deposited LiCoO2 Cathodes for Lithium-Ion Thin-Film Batteries
S. MITRA, Department of Physics, Astronomy, and Materials Science, Missouri State University, Springfield, MO, USA
The growing need for sustainable energy has driven advances in high-energy-density materials for next generation storage materials. LiCoO₂ thin films were fabricated on quartz and stainless steel substrates (SS) using pulsed laser deposition (PLD) at 400, 650, and 700 °C under oxygen pressures of 10 and 100 mTorr. X-ray confirmed the R3m structure and Raman spectroscopy identified characteristic vibrational modes and multiphase features. UV-Vis analysis showed optical bandgaps between 2.27 eV and 2.52 eV for films on quartz. Electrical studies revealed enhanced DC conductivity at higher oxygen pressure ranging from 4.5 × 10⁻⁸ to 4.1 × 10⁻³ S cm⁻¹. The highest discharge capacity of 30.10 µA h cm⁻² µm⁻¹ was obtained for the SS film grown at 650 °C and 10 mTorr. The discharge capacity remained stable over ten cycles, confirming the films’ structural integrity and electrochemical reliability.
FE-1:L21 Density Functional Theory-Guided Design of High-Performance Electrodes for Metal-Ion Batteries
V. BARONE, Department of Physics, Central Michigan University, Mount Pleasant, MI, USA
Advancing energy storage technologies hinges on the rational design of high-performance electrode materials. Density Functional Theory (DFT) is as a powerful computational tool for probing the atomic-scale properties that govern electrochemical behavior in metal-ion batteries. This talk will explore how DFT enables predictive modeling of electrode materials, offering computational insights into structure stability, voltage profiles, electronic structure, and charging/discharging kinetics. By integrating DFT with experimental data and machine learning approaches, we can accelerate the discovery of novel compounds and optimize existing materials for enhanced capacity, stability, and sustainability. Case studies will highlight recent successes in designing electrodes for lithium, sodium, and multivalent ion systems, demonstrating the significant role of computational methods in battery research. The presentation aims to bridge theory and application, showcasing how DFT can contribute to the development of next-generation energy storage solutions.
FE-1:IL23 Zn/Li Dual-Ion Batteries with Water-in-Salt Electrolytes
L. KAVAN, J. Heyrovsky Institute of Physical Chemistry, Czech Academy of Sciences, Prague 8, Czech Republic
Aqueous dual-ion (Zn/Li) batteries combine safety and sustainability, emerging as strong contenders to conventional Li-ion systems. They merge the abundance and safety of the Zn/water interface with the high energy density of lithium oxides or phosphates. Challenges of aqueous electrolytes, i.e., gas evolution, corrosion, and Zn dendrites are mitigated by water-in-salt electrolytes (WiSE), where the salt-to-water mass ratio exceeds unity. This study examines materials, substrates, electrodes, and electrolytes relevant to Zn/Li dual-ion batteries using ZnCl₂-based WiSE. Titanium shows the widest electrochemical stability window, while carbon becomes unstable above 2.2 V vs Zn, limiting its use in high-voltage electrodes like LiMnPO₄. Conversely, carbon-coated LiFePO₄ is stable, showing good capacity and cycling, with its potential shifting positively with Li concentration. Impurities such as Mn in ZnCl₂ can mimic LiMnPO₄, complicating analysis. Intentional Mn(II) addition yields redox-flow-like behavior, with solution-based Mn(II, III, IV and VII) charge storage. WiSE with Au(III) shows similar electrochemical responses.
Funded by the project "The Energy Conversion and Storage" No. CZ.02.01.01/00/22_008/0004617 by Programme Johannes Amos Comenius.
Session FE-2 Supercapacitors
FE-2:IL25 Pulsed Chronoamperometric Electrodeposition of Manganese Oxides for Electrochemical Capacitors
F.J. MUJAMAMMI, S.W. DONNE, Discipline of Chemistry, University of Newcastle, Callaghan NSW, Australia
Electrochemical capacitors are typified by excellent high power output but limited energy density, making them ideal for pulse electrical applications. To improve their energy density pseudocapacitive materials have been developed and implemented, making use of facile charge transfer (redox) kinetics, rather than physical charge separation, to store energy. Manganese oxides are a structurally and morphologically diverse family of materials with a long history of use in energy storage and conversion systems. They are of particular interest in electrochemical capacitors because of their facile charge transfer kinetics, energy density and low cost. Herein we describe a pulsed chronoamperometric electrodeposition technique for controlling the morphology of manganese dioxide thin films for use as electrodes in electrochemical capacitors. The nature of the pulse sequence involves alternating deposition and stripping processes designed to tune the resultant material properties. Variables such as the deposition and stripping potentials, pulse duration and duty cycle, as well as number of cycles have been explored for their effects on morphology. Such films are also ideal for mechanistic analysis, particularly when combined with advanced electrochemical characterization.
FE-2:L27 Tunable Dielectric Behavior of Lignin:Unlocking Supercapacitive Behavior for Eco-Friendly Electronics
M. AMBRICO1, S. DE STEFANO2, O. DURANTE2, R. D'ORSI3, D. ACETO1, P.F. AMBRICO1, N. MARTUCCIELLO4, F. GIUBILEO4, S. RIVAS5, A. OPERAMOLLA3, A. DI BARTOLOMEO2, 1CNR – ISTP, Institute for Plasma Science and Technology, Bari, Italy; 2Department of Physics “E.R. Caianiello”, University of Salerno, Fisciano (Sa), Italy; 3Department of Chemistry and Industrial Chemistry, University of Pisa, Pisa, Italy; 4CNR-SPIN, Salerno Unit, Fisciano (Sa), Italy; 5Department of Chemical Engineering, Faculty of Science of Ourense, University of Vigo, Ourense, Spain
Lignin, a sustainable by-product of pulping processes, is gaining attention for advanced electronic applications due to its rich aromatic structure and functional groups. This study compares three lignin types—two Kraft-derived (L1, L2) and one organosolv-extracted from Cynara cardunculus (L3)—as active layers in interdigitated electronic devices. Using Current Voltage, Impedance and Broadband Spectroscopy together with the representation via the Complex Power analysis, the study evaluates how structural and chemical differences affect charge transport and dielectric relaxation. Results show that: L1 has a compact morphology and high polymerization, limiting charge mobility; L2 exhibits a fibrous structure with more carboxyl groups and ash, enhancing conductivity and capacitance; L3 offers a balanced profile with abundant aliphatic hydroxyl groups. As a major finding, lignin’s tunable properties and its potential as a versatile dielectric material with charge storage and supercapacitive behavior, supporting its use in sustainable electronics.
FE-2:IL28 Advanced Electrochemical Characterization Techniques for Revealing Charge Storage Mechanisms in Nanostructured Materials for Energy Storage Applications
P. SIMON, University of Toulouse, Materials Sciences Department, Toulouse, France
A deep understanding of electrolyte ion dynamics—both at the electrolyte/electrode interface and within the bulk of porous electrode materials—is essential for improving charge storage in electrochemical energy‐storage systems such as batteries and supercapacitors. However, deciphering the solvent-ions interaction and ions-electrode interaction upon the processes of adsorption, intercalation, extraction and transportation of ions in host materials remains challenging as all these processes occurs at the nanoscale or in confined environments. In this presentation, we will show how advanced electrochemical techniques can be employed to characterize ionic and electronic transport at the nanometer scale in model materials, including 3D porous carbons, 2D reduced graphene oxide, and metal carbides (MXenes). We will demonstrate that the confinement of electrolytes within sub-nanometer pores profoundly alters their solvation state, leading to unique and advantageous charge‐storage properties. Understanding confined electrochemical systems and coupling between chemical, electrochemical, and transport processes under confinement may open tremendous opportunities for energy applications in the future.
FE-2:IL29 In-operando Understanding Degradation Processes in Electrochemical Supercapacitors
A. BALDUCCI, R. KOST, Friedrich Schiller University Jena, Institute for Technical Chemistry and Environmental Chemistry and Center for Energy and Environmental Chemistry Jena (CEEC Jena), Jena, Germany
Electric double-layer capacitors (EDLCs) are considered among the most important energy storage devices utilized in our daily lives. They display high specific power, the advantages of fast charge and discharge times, and a long operational lifetime. The aging of EDLCs, which typically leads to loss of capacitance and increases in resistance is a very complex process that involves various failure mechanisms, each playing a crucial role. These mechanisms involve structural and chemical changes, material dissolution, and corrosion of metal current collectors during cell operation. In the past, most effort has been directed towards examining and understanding the aging occurring on the electrodes of EDLCs. On the other hand, less attention has been dedicated to the processes occurring on the electrolyte and it is not fully clear how the different electrolyte decomposition processes affect the performance of EDLC’s. In this work we report about some of our latest studies dedicated to the investigation of the degradation processes occurring in the electrolyte of EDLCs. Particularly, we will report about the use of post-mortem and in-operando gas chromatography-mass spectrometry (GC-MS) for the investigation of the solvent degradation in EDLCs.
FE-2:IL30 Modelling Nanoporous Carbons for Capacitive Storage
A. SERVA, M. SALANNE, Sorbonne Université, CNRS, Physico-chimie des Electrolytes et Nanosystémes Interfaciaux, Paris, France
Nanoporous carbon-based supercapacitors have been a major research topic over the past two decades. Combined with spectroscopy and electrochemistry, molecular simulations offer valuable insights into their charging mechanism at the molecular level. Our group has developed a classical molecular dynamics code to simulate these systems, in which a constant potential difference is applied between the electrodes. In the recent years, we have also introduced explicit all-atom models for the electrolytes, and polarization effects, improving simulation accuracy. This approach has been applied to study complex carbide-derived carbons with 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonyl imide ionic liquid electrolyte, yielding integral capacitances in quantitative agreement with experiments and revealing asymmetric charging mechanism between positive and negative electrodes. However, in these works the influence of the electrode flexibility was not considered. In our latest work, we address this by coupling constant potential classical MD with a state-of-the-art machine learning potential for carbon. We show that flexible electrodes shorten charging time by a factor of 3 through enhanced in-pore diffusivity, while yielding capacitance values within the experimental range.
FE-2:IL31 Redox or Non-redox? – Strategies for Hybrid Metal-ion Capacitors Development
K. FIC1,2, A. MAĆKOWIAK1, P. JEŻOWSKI1, P. GALEK1, P. BUJEWSKA1, YUKIKO MATSUI2, KAZUNARI SOEDA2, MASASHI ISHIKAWA2, 1Poznan University of Technology, Poznan, Poland; 2Kansai University, Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Suita, Japan
In our approach, we tried to develop a novel method to assembly the metal-ion capacitor in one simple step, without adding any additive to the electrode material. In our concept, the electrolyte is the source of alkali metal (Li, Na, and K) and allows for single-step capacitor assembly. In addition to presenting our latest results, our contribution aims to provide a comprehensive insight into the application of redox-active electrolytes in hybrid metal ion-capacitors. Apart from typical electrochemical measurements, various in-situ and operando techniques such as Raman spectroscopy, Electrochemical Dilatometry (ECD), Gas Chromatography coupled with Mass Spectrometry (e-GCMS) and On-line Internal Pressure Measurement (OIPM) were applied for determination of the charge storage phenomena and ageing factors. This paper will also discuss certain aspects of the electrolyte (concentration, kind of solvent) that affect the capacitor performance in the long-term perspective.
FE-2:IL32 Solid-Electrolyte Interphase (SEI) Formation on Graphite Electrodes at High Rates
WATARU SUGIMOTO, O. GÓMEZ ROJAS, Shinshu University, Institute for Aqua Regeneration, Ueda, Japan
Lithium-ion capacitors (LICs), which typically couple a capacitive-positive electrode and a battery-type positive electrode are promising solutions for high-rate energy storage. The solid-electrolyte interphase (SEI) formation under rapid cycling is underexplored compared to LIBs, thus leaving key interfacial processes still unknown (or discussed based on LIB data). Here we use a water-stable graphite anode consisting of a laminated, oversized, pre-lithiated LixC6 anode | glass-fiber separator soaked with EmimFSI–LiFSI or P13FSI–LiFSI | LISICON-type glass-ceramic, which is paired with an activated-carbon positive electrode immersed in 1.0 M Li2SO4 to explore the (pre-)lithiation of graphite and SEI formation at high rates. P13FSI-based electrolytes exhibited longer cycling capabilities than the EmimFSI-based counterparts. The P13FSI-based electrolytes showed lower post-cycling interfacial/charge-transfer resistance. When coupled with 2.5 vol% VC, a stable, organic-rich SEI was obtained. On the other hand, EmimFSI-based electrolytes yielded progressive accumulation of inorganic reduction products, increasing impedance, and shorter operational lifetime.
FE-2:IL33 Supercapacitors for Iontronics
S. KASKEL, TU Dresden, Dresden, Germany
Supercapacitors stand out as high power devices for ultrafast energy storage. A new paradigm is to use ion electroadsorption devices for capacitive logic information processing and power management logic in autonomous devices. In living organisms, ions and chemical transmitters are involved in signaling, managing logic operations and memory, evolutionary optimized in terms of energy-efficiency. Recently, we reported the first switchable ultracapacitor devices emulating discrete electronic circuit elements (diode, transistor) and demonstrated logic operations, a key step towards ultracapacitor-based ion information signaling and processing. We report the conceptual design and realization of capacitive logic gates (AND, OR, NAND, etc.) based on ion electroadsorption in nanoporous carbons by integrating multiple switchable EDLC elements into monolithic microdevices. Ultracapacitor logic gates constitute the basis for novel ion-based computing technologies to reduce energy dissipation in computing architectures and enable on-chip power management in autonomous microelectronic and biointerfacing devices in future.
FE-2:IL34 Supercapacitive Microbial Fuel Cells: Processes and Devices
F. SOAVI, M. CASTELLUCCI, C.E. PAROLIN, University of Bologna, Bologna, Italy; C. SANTORO, University of Milano-Bicocca, Milano, Italy
Microbial Fuel Cells (MFCs) convert organic compounds present in wastewater into electricity through electroactive microorganisms that oxidize these organics at the anode, while oxygen reduction occurs at the cathode to complete the reaction. Despite their great potential, MFCs must be further improved in terms of power output and performance quality to become a technology capable of significantly transforming the water and energy landscape. Here, we report on different strategies pursued to address these challenges: (i) the exploitation of the inherent capacitive behavior of MFC electrodes, which was also investigated by electrochemical impedance spectroscopy (EIS), and (ii) the smart integration of MFCs with supercapacitors, properly designed to maintain the green footprint of MFCs while achieving short recharge times and high power output.
1. L. Caizán-Juanarena, et al. Biotechnol. Adv. 39 (2020) 107456; 2. F. Poli, et al. J. Power Sources 564 (2023) 232780.