Tag Archive for: Keyhole 9 MHz QCM

Publication on AWSensors technology

Operando Tracking of Resistance, Thickness, and Mass of Ti3C2Tx MXene in Water-in-Salt Electrolyte

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Authors: Audrey Perju, Danzhen Zhang, Ruocun John Wang, Pierre-Louis Taberna, Yury Gogotsi, Patrice Simon

Journal:  Adv. Energy Mater.

Abstract: MXenes are among the fastest-growing families of 2D materials, promising for high-rate, high-energy energy storage applications due to their high electronic and ionic conductivity, large surface area, and reversible surface redox ability. The Ti3C2Tx MXene shows a capacitive charge storage mechanism in diluted aqueous LiCl electrolyte while achieving abnormal redox-like features in the water-in-salt LiCl electrolyte. Herein, various operando techniques are used to investigate changes in resistance, mass, and electrode thickness of Ti3C2Tx during cycling in salt-in-water and water-in-salt LiCl electrolytes. Significant resistance variations due to interlayer space changes are recorded in the water-in-salt LiCl electrolyte. In both electrolytes, conductivity variations attributed to charge carrier density changes or varied inter-sheet electron hopping barriers are detected in the capacitive areas, where no thickness variations are observed. Overall, combining those operando techniques enhances the understanding of charge storage mechanisms and facilitates the development of MXene-based energy storage devices.

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Publication on AWSensors technology

Operando Gravimetric and Energy Loss Analysis of Na3V2(PO4)2F3 Composite Films by Electrochemical Quartz Microbalance with Dissipation Monitoring

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Authors: Jeronimo Mirand, Pierre-Louis Taberna, Patrice Simon

Journal: ACS Nano

Abstract: The rising demand for energy storage calls for technological advancements to address the growing needs. In this context, sodium-ion (Na-ion) batteries have emerged as a potential complementary technology to lithium-ion batteries (Li-ion). Among other materials, Na3V2(PO4)2F3 (NVPF) is a promising cathode for Na-ion batteries due to its high operating voltage and good energy density. In order to further characterize the (dis)charge behavior of NVPF, the electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) was employed to track both the frequency and dissipation loss changes at the electrode/electrolyte interface. The electrode composite preparation proved to be crucial for extending the potential window to both Na3V2(PO4)2F3/Na2V2(PO4)2F3 and Na2V2(PO4)2F3/Na1V2(PO4)2F3 domains. Composites prepared with rawNVPF powder (1–20 μm particles) and polyvinylidene fluoride (PVDF) binder (raw-NVPF:PVDF) exhibited large dissipation changes during (dis)charging, attributed to the soft viscoelastic nature of the binder and substantial hydrodynamic interaction caused by the large particles. On the other hand, composites prepared by sieved NVPF particles (<1 μm particles) with sodium carboxymethyl cellulose (NaCMC) binder (sieved-NVPF:NaCMC) showed rigid properties, enabling an extended and more accurate gravimetric analysis. This allowed for the determination of a linear charge-to-mass relationship for the full potential window of NVPF, reflecting the potential independent insertion/deinsertion of bare Na ions (23 g·mol–1). Additionally, reversible dissipative changes were observed for the Na3V2(PO4)2F3/Na2V2(PO4)2F3 transition, with no further dissipative changes observed during the Na2V2(PO4)2F3/Na1V2(PO4)2F3 process

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Publication on AWSensors technology

Unlocking self-discharge: Unveiling the mysteries of electrode-free Zn-MnO2 batteries with advanced in situ techniques in mild acid aqueous electrolytes

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Authors: Arvinder Singh, Lamia Ouassi, Keho Allemang, Jean-François Lemineur, Ozlem Sel, Frédéric Kanoufi, Christel Laberty-Robert

Journal: Journal of Power Sources 2025

Abstract: We introduce a novel approach to Zinc-MnO2 battery architecture utilizing a 3D network of carbon nanofibers as both current collector and electrode material, promising enhanced performance and longevity for large-scale energy storage. Employing mild aqueous electrolytes, we address the challenge of managing self-discharge, crucial for short-term energy storage. Advanced coupled characterization techniques, including in-situ EQCM (Electrochemical Quartz Crystal Microbalance) and high-resolution optical microscopy, elucidate self-discharge mechanisms across over multiple length scales. Findings reveal that the self-discharge is mainly at the zinc electrode due to concomitant dissolution of Zinc (corrosion) and HER (Hydrogen Evolution Reaction) phenomena. Interestingly, the corrosion current was estimated irrespective of charging protocol and remains consistent, indicating the independence of zinc corrosion kinetics from the length scale. Finally, the morphology of the zinc layer appears to be critical, suggesting that self-discharge is primarily a chemical process. This innovative design strategy offers the potential for high-performance Zinc-MnO2 batteries with extended cycle life to meet the requirements of large-scale energy storage applications.

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Publication on AWSensors technology

Study of the inhibition efficiency of DTPMPA on calcium carbonate formation via advanced tools

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Authors: Soumaya Nouigues, Nelson Acevedo, Yasser Ben Amor, Christel Laberty-Robert, Hubert Perrot, Hélène Cheap-Charpentier

Journal: Desalination

Abstract: The inhibition efficiency of a scale inhibitor, named diethylene triamine penta (methylene phosphonic acid) (DTPMPA), was evaluated using fast controlled precipitation (FCP) method, electrochemical quartz crystal microbalance (EQCM), quartz crystal microbalance with dissipation (QCM-D) and pre-scaled quartz crystal microbalance (SQCM). The results showed that DTPMPA delayed the CaCO3 precipitation and decreased the precipitation rate of the CaCO3 formation in solution and on a metallic surface, depending on the inhibitor concentration. In some cases, it could completely inhibit CaCO3 formation. CaCO3 precipitation was completely inhibited in solution and on a metallic surface in the presence of 0.5 mg⋅L−1 and 4 mg⋅L−1 DTPMPA, according to FCP and EQCM results, respectively. The morphology and composition of CaCO3 crystals formed were studied using SEM and XRD showing that the presence of the inhibitor promoted the formation of calcite. This is the first time that the influence of an organic inhibitor was studied using the combination of QCM methods, where the results revealed a reduction of the surface coverage by a CaCO3 layer as the inhibitor concentration increased. The activation energies were calculated in the presence of DTPMPA and indicated that the inhibitor retarded the scaling process.

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Publication on AWSensors technology

On the Electrochemical Activation of Nanoporous Reduced Graphene Oxide Electrodes Studied by In Situ/Operando Electrochemical Techniques

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Authors: María del Pilar Bernicola, Mailis Lounasvuori, Jessica Padilla-Pantoja, Jose Santiso, Catherine Debiemme-Chouvy, Hubert Perrot, Tristan Petit, Jose A. Garrido, Elena del Corro

Journal: Advanced Functional Materials

Abstract: Due to the difficult access of the electrolyte into the nanoconfined space of nanoporous reduced graphene oxide (rGO) electrodes, achieving the optimal electrochemical performance of these devices becomes a challenge. In this work, the dynamics of interfacial-governed phenomena are investigated during a voltage-controlled electrochemical activation of nanoporous rGO electrodes that leads to an enhanced electrochemical performance in terms of areal capacitance and electrochemical impedance. In situ/operando characterization techniques are used to reveal the dynamics of the irreversible material changes introduced during the activation process, including ionic diffusion and water confinement within the nanopores, along with the reduction of oxygenated groups and the decrease of the rGO interlayer distance. Furthermore, operando techniques are used to uncover the origin of the complex polarization-dependent dynamic response of rGO electrodes. The study reveals that the reversible protonation/deprotonation of remaining functional groups and the cation electro-adsorption/desorption process in the graphene basal plane govern the pseudocapacitive performance of nanoporous rGO electrodes. This work brings new understanding of the complex interplay between surface chemistry, ion confinement, and desolvation processes occurring during electrochemical cycling in nanoporous rGO electrodes, offering new insights for designing high-performing electrodes based on nanoporous rGO.

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Publication on AWSensors technology

Highly Ordered Graphene Polydopamine Composite Allowing Fast Motion of Cations: Toward a High-Performance Microsupercapacitor

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Authors: Adnane Bouzina, René Meng, Cyrille Bazin, Hubert Perrot, Ozlem Sel, Catherine Debiemme-Chouvy

Journal: Adv. Mater. Interfaces (2023)

 

Abstract

The simple and eco-friendly preparation of microsupercapacitor remains a great challenge. Here are presented the preparation and the characterizations of an all-solid symmetric micro-supercapacitor based on a new composite formed of highly ordered graphene sheets due to the presence of polydopamine between the layers, which present a d-spacing of 0.356 nm. This graphene-polydopamine composite is prepared by electroreduction of graphene oxide (GO) followed by the electrooxidation of dopamine added into the initial solution, i.e., after GO reduction. In Na2SO4 solution, this composite material shows excellent capacitance and stability even at a high scan rate (2 V s−1) and a very low relaxation time (τ0) of 62 ms. This value is in very good agreement with the high transfer kinetic and low transfer resistance values of the ions implied in the charge storage process (Na+·2H2O and Na+) determined by ac-electrogravimetry. Finally, it is shown that the all-solid micro-supercapacitor (interdigitated electrodes obtained using a CO2 laser and Na2SO4/PVA hydrogel) prepared with this new composite delivers a remarkable energy density of 6.36 mWh cm−3 for a power density of 0.22 W cm−3 and exhibits excellent cycling stability (98% of retention after 10 000 cycles at 2 V s−1).

 

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Publication on AWSensors technology

Interface Properties of 2D Graphene–Polydopamine Composite Electrodes in Protic Ionic Liquid-Based Electrolytes Explored by Advanced Electrogravimetry

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Authors: Adnane Bouzina, Hubert Perrot, Catherine Debiemme-Chouvy, and Ozlem Sel

Journal: ACS Appl. Energy Mater. (2022)

 

Abstract

A fundamental understanding of the processes occurring at the electrode/electrolyte interfaces is of paramount importance to enhance the performance of energy storage devices. Addressing this issue requires suitable characterization tools, due to the complex nature of such interfaces. By means of electrochemical quartz crystal microbalance (EQCM) and its advanced mode, the so-called ac-electrogravimetry, herein, we report on the interfacial properties of two-dimensional (2D) graphene–polydopamine (ERGO-PDA) composite electrodes in diverse electrolyte compositions including a protic ionic liquid (PIL), pyrrolidinium hydrogen sulfate [Pyr+][HSO4–]. We have performed a comparative study in a [Pyr+][HSO4–]–water binary mixture in the absence and presence of Na2SO4 and compared it with the interfacial behavior of ERGO-PDA in a 0.5 M Na2SO4 (pH = 2) pristine electrolyte. Our EQCM and ac-electrogravimetric analyses reveal that the [Pyr+] ions, due to their chaotropic nature, inhibit the approach of kosmotropic Na+ ions and water molecules to the interface, suppressing the contribution of electrodragged water molecules, substantially observed in the case of pristine aqueous electrolyte. Despite the dissimilarity of the charge compensation process occurring in the presence of [Pyr+][HSO4–], the ERGO-PDA electrode is able to maintain similar cycling stability (99% for 10,000 cycles at 1000 mV·s–1) and specific capacitance values (325 F·cm–3) compared with the pristine aqueous electrolyte, with the advantage of superior energy density (16.3 versus 8.7 mWh·cm–3) due to a noticeably enlarged potential window in [Pyr+][HSO4–]–water binary mixtures.

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Publication on AWSensors technology

Interfacial charge storage mechanisms of composite electrodes based on poly(ortho-phenylenediamine)/carbon nanotubes via advanced electrogravimetry

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Authors: El Mahdi Halim, Rezan Demir-Cakan, Hubert Perrot, Mama El Rhazi, Ozlem Sel

Journal: The Journal of Chemical Physics (2022)

 

Abstract

To reach a deeper understanding of the charge storage mechanisms of electrode materials is one of the challenges toward improving their energy storage performance. Herein, we investigate the interfacial ion exchange of a composite electrode made of carbon nanotube/poly( ortho-phenylenediamine) (CNT/P oPD) in a 1M NaCl aqueous electrolyte via advanced electrogravimetric analyses based on electrochemical quartz crystal microbalance (EQCM). Classical EQCM at different scan rates of the potential revealed the complex electrogravimetric behavior likely due to multi-species participation at different temporal scales. Thereafter, in order to better understand the behavior of each species (ions, counter ions, and co-ions) in the charge compensation mechanism, the electrogravimetric impedance spectroscopy analysis (also called ac-electrogravimetry) was pursued. Ac-electrogravimetry revealed the role of each species where Na + cations and Cl − anions as well as protons participate in the charge compensation mechanism of the CNT/P oPD composite with different kinetics and proportions. The water molecules with opposite flux direction with the cations are also detected, suggesting their exclusion during cationic species transfer. Having analyzed ac-electrogravimetry responses in depth, the synergistic interaction between the CNT and P oPD is highlighted, revealing the improved accessibility of species to new sites in the composite.

 

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Scientific publication

Interface evolution and performance degradation in LiCoO2 composite battery electrodes monitored by advanced EQCM

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Authors: Wanli Gao, Christel Laberty-Robert, Natacha Krins, Catherine Debiemme-Chouvya, Hubert Perrot and Ozlem Sel.
Journal: Electrochimica Acta (2022)

 

Abstract

Unravelling the underlying reasons for degradation mechanism of battery materials is of great fundamental and practical importance. For a classical electrode consisting of an active material, a conductive additive, and a polymeric binder, its capacity fading is commonly related with (i) mechanical degradation of polymeric binder and/or (ii) structural and compositional degradation of active materials. The former is more relevant for electrodes showing volume expansion and represented by the progressive breakage of polymeric binder network during battery operation, leading to the dissolution of the other two components into electrolytes. The latter is generally reflected by an irreversible phase transition in active materials, which may affect the species exchanged at the electrode/electrolyte interface and their interfacial transfer dynamics. By employing a coupled methodology pairing electrochemical techniques with piezoelectric probes derived from quartz crystal microbalance (QCM), this work reports on the evolution of the interfacial processes during electrochemical cycling and correlates to the performance degradation of the electrodes. Shown on a LiCoO2 (LCO) composite electrode as a model system, it was revealed that bare Li+ without a hydration sheath plays a dominant role in charge balance irrespective of the aging degree of the electrode under the experimental conditions of this work. However, Li+ transfer is closely accompanied with free H2O molecules with a Li+:H2O ratio around 10:1 at a polarization state close to LCO redox potential (0.65 V vs. Ag/AgCl). This ratio persists in all cycled electrodes with gradually faded interfacial transfer kinetics of Li+ and H2O along cycling. Such a fading in species interfacial transfer kinetics driven by the surficial evolution from LiCoO2 to CoO plays a major role in the electrode performance degradation during cycling.

LiCoO2 composite battery electrodes

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Scientific publication

Ion Dynamics at the Carbon Electrode/Electrolyte Interface: Influence of Carbon Nanotubes Types

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Authors: Freddy Escobar-Teran, Hubert Perrot and Ozlem Sel.
Journal: Materials (2022)

 

Abstract

Electrochemical quartz crystal microbalance (EQCM) and AC-electrogravimetry methods were employed to study ion dynamics in carbon nanotube base electrodes in NaCl aqueous electrolyte. Two types of carbon nanotubes, Double Wall Carbon Nanotube (DWCNT) and Multi Wall Carbon Nanotube (MWCNT), were chosen due to their variable morphology of pores and structure properties. The effect of pore morphology/structure on the capacitive charge storage mechanisms demonstrated that DWCNT base electrodes are the best candidates for energy storage applications in terms of current variation and specific surface area. Furthermore, the mass change obtained via EQCM showed that DWCNT films is 1.5 times greater than MWCNT films in the same potential range. In this way, the permselectivity of DWCNT films showed cation exchange preference at cathode potentials while MWCNT films showed anion exchange preference at anode potentials. The relative concentration obtained from AC-electrogravimetry confirm that DWCNT base electrodes are the best candidates for charge storage capacity electrodes, since they can accommodate higher concentration of charged species than MWCNT base electrodes.

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