Thierry Brousse

Thierry Brousse
University of Nantes | UNIV Nantes · Jean Rouxel Institute of Materials

PhD

About

258
Publications
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12,786
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Publications

Publications (258)
Article
In nanosized FeWO4 electrode material, both Fe and W metal cations are suspected to be involved in the fast and reversible Faradaic surface reactions giving rise to its pseudocapacitive signature. In order to fully understand the charge storage mechanism, a deeper insight into the involvement of the electroactive cations still has to be provided. T...
Article
Full-text available
In this work we have investigated the charge storage mechanism of MnO2 electrodes in ionic liquid electrolytes. We show that by using an ionic liquid with a cation that has the ability to form hydrogen bonds with the active material (MnO2) on the surface of the electrode, a clear faradaic contribution is obtained. This situation is found for ionic...
Article
Full-text available
The Internet of Things, enabled by a worldwide network of interconnected sensors, is limited in its large-scale deployment of nomadic miniaturized devices due to the bounds of energy self-sufficiency. One possible solution, albeit challenging, is constructing on-chip pseudocapacitive micro-supercapacitors. Herein, we achieve the collective fabricat...
Preprint
Full-text available
In nano-sized FeWO<sub>4</sub> electrode material, both Fe and W metal cations are suspected to be involved in the fast and reversible Faradaic surface reactions giving rise to its pseudocapacitive signature. As for any other pseudocapacitive materials, to fully understand the charge storage mechanism, a deeper insight into the involvement of the e...
Article
Two asymmetric aqueous electrochemical capacitors operated in 5 M LiNO3 are reported: C/Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) and FeWO4/BSCF, with activated carbon and FeWO4 (synthesized by a precipitation method) as negative electrodes, respectively, and BSCF (synthesized by a modified glycine-nitrate process) as positive electrodes. These two devices w...
Article
We demonstrate an asymmetric supercapacitor in a potassium acetate-based water-in-salt electrolyte, where 2-D titanium carbide MXene and manganese oxide were used as negative and positive electrode materials, respectively. Use of water-in-salt electrolyte enables the assembled asymmetric device to be operated up to a cell voltage of 2.2 V, which ov...
Article
This paper describes the design and tests of aqueous hybrid energy storage devices based on activated carbon negative electrode and LiMn2O4 (spinel) positive electrode. For this study activated carbons from two different sources are selected and are further improved by grafting with electroactive anthraquinone molecules. The electrolyte solution is...
Article
To date, the design of high temperature electrochemical double layer capacitors (EDLCs) remains a challenge more specifically related to the electrolyte. The electrochemical performance of EDLC can be tuned by the temperature, and a better performance can be achieved at higher temperature if all the components are well suited to this purpose. Subse...
Presentation
The specific capacitance of electrochemical capacitors (ECs) directly depends on the porous morphology of the active area. The control of the surface area is thus a key parameter to control the electrolyte accessibility to the surface of the active material, in order to increase the charge storage. In this view, we demonstrate that the glancing ang...
Presentation
Transition metal nitrides are suitable materials for electrochemical capacitors (ECs), exhibiting good electrochemical performance and good cycling life stability; moreover, they are easy to synthesize, especially by magnetron sputtering. However, the dense nature of the coating deposited by sputtering is one of the limiting factors to achieve high...
Article
An industry‐relevant method for pre‐lithiation of lithium‐ion capacitors to balance the first charge irreversibility is demonstrated, which addresses the prime bottleneck for their market integration. Based on a composite positive electrode that integrates pyrene monomers and an insoluble lithiated base, Li3PO4, a “cascade‐type” process involving t...
Article
Full-text available
Micro-supercapacitors, a class of miniaturized electrochemical capacitors, are an attractive solution to power smart and connected sensors for Internet of Thing (IoT)applications. Unfortunately, to propose on chip micro-supercapacitors with high technological readiness level, the deposition of electrode materials on large-scale substrate is challen...
Preprint
div>Herein, we report a improved method for the physical grafting of 1-nitropyrene (Pyr-NO2) onto highly graphitized carbon onion. This is achieved through a lowering of the onset potential of the pyrene polymerization via in situ reduction of the NO2 group. The additional redox activity pertaining to the reduced NO2 enables exceeding the faradaic...
Article
Full-text available
The fabrication of miniaturized electrochemical energy storage systems is essential for the development of future electronic devices for Internet of Thing applications where connected devices are increasingly deployed in our daily life. On chip micro-supercapacitors are an attractive solution to fulfill the energy requirements of autonomous, smart,...
Article
Factors affecting the cyclability of the Fe-substituted LiCoPO4 (LiCo0.8Fe0.2PO4, LCFP) material were elucidated, including both the structural and electrode/electrolyte stability. Electrochemical characterization of the synthesized LCFP nanoparticles lends clear evidence for improved electrochemical stability of LCP, as well as enhanced rate capab...
Article
The preparation of MnPO4 ·H2O and its study as electrode material for electrochemical capacitors is reported. The charge storage mechanism is pseudocapacitive and involves insertion of hydroxyl ions into the 1Dtunnels of the crystalline structure of MnPO4 · H2O, that together with the diverse functional groups of this manganese phosphate allows the...
Article
Full-text available
Nanocomposites of Ni(OH)2 or NiO have successfully been used in electrodes in the last five years, but they have been falsely presented as pseudocapacitive electrodes for electrochemical capacitors and hybrid devices. Indeed, these nickel oxide or hydroxide electrodes are pure battery-type electrodes which store charges through faradaic processes a...
Article
Full-text available
Micro‐supercapacitors (MSC) are considered as promising miniaturized electrochemical energy storage devices for Internet of Things applications. Unfortunately, the technological readiness level of these devices is still at the lab scale with the development of individual prototypes due to the difficulty to produce high performance porous electrode...
Article
Full-text available
Vanadium nitride (VN) films with different thicknesses were deposited over polished silicon substrate using DC plasma reactive sputtering. These films were tested as electrodes for electrochemical capacitorsin a 1M KOH aqueous electrolyte solution. The electrodes show excellent specific capacitance with maximum areal capacitance value of 238.2 mF.c...
Article
Full-text available
The electrochemical performance of electrochemical capacitors can be improved with electroactive quinone molecules. Systems based on redox active electrolyte as well as physisorbed and chemically grafted molecules have been investigated. In all these cases, carbon materials were used as substrate and electrode material. This short review will mainl...
Article
The effect of surface chemistry of reactive sputtered TiN electrodes in the electrochemical capacitors (ECs) was investigated. The TiN films were produced on vertically aligned carbon nanotubes. X-ray photoelectron spectroscopy analysis revealed surface defects generation with no effect on morphology. Cyclic voltammetry experiments were performed i...
Article
Full-text available
Since the early use of RuO2-based electrodes in electrochemical capacitors, so called supercapacitors, metal oxides have always attracted much attention as pseudocapacitive electrode materials for such energy storage devices. Although the literature is well documented about electrode materials based on single metal oxides, polycationic oxides have...
Article
Hybrid supercapacitors, which combine a capacitive negative electrode and a faradaic positive electrode operating in an aqueous media, have many potential applications such as frequency regulation on the electrical grid, in particular when used in conjunction with intermittent energy sources. The purpose of this work is to study alternative designs...
Article
Ba0.5Sr0.5CoxFe1-xO3-d phases, with 0.75 < x < 0.90, so-called BSCFs, were investigated as pseudocapacitive electrode materials. These polycationic oxide phases were prepared by a modified glycine-nitrate process and show the same perovskite structural arrangement and similar morphological characteristics in the whole series. The electrochemical pe...
Article
Full-text available
Lithium-ion capacitors (LICs) shrewdly combine a lithium-ion battery negative electrode capable of reversibly intercalating lithium cations, namely graphite, together with an electrical double-layer positive electrode, namely activated carbon. However, the beauty of this concept is marred by the lack of a lithium-cation source in the device, thus r...
Article
Abstract We report experimental evidence for the specific Li-storage at turbostratic graphene edges of a well-known and cheap Super P® carbon black (Csp) material, which is usually used as a conductive additive in composite electrodes. Indeed, operando XRD and HR-TEM consistently demonstrate Li insertion occurs with zero expansion of graphene layer...
Chapter
Electrochemical capacitors are energy storage devices that have intermediate energy and power densities between those of batteries (high energy) and dielectric capacitors (high power). In this chapter, the distinctions between these different devices, as well as emerging devices such as lithium-ion capacitors, are presented in terms of electric and...
Article
A large data set of XAS Manganese K-edge spectra has been collected operando and studied upon the electrochemical oxidation of the promising Li-ion batteries anode material Li7MnN4. Using chemometric tools such as PCA and MCR-ALS, three independent environment spectra were insulated. Based on the faradaic yield and well-chosen comparison of absorpt...
Article
Full-text available
Vanadium nitride (VN) was deposited, by DC-sputtering, on vertically aligned CNTs template for nano-structuration purpose. This led to a fabrication of hierarchically composite electrodes consisting of p orous and nanostructured VN grown on vertically aligned CNTs in a form of nano-trees like electrode for micro-supercapacitor application. The ele...
Article
Full-text available
The fabrication of high-performance on-chip 3D micro-supercapacitors (MSCs) based on MnO2 pseudocapacitive binder-free thin film electrodes (<500 nm thick) with interdigitated topology is reported. An original technological process easily scalable to pilot production line is proposed on 3 in. silicon wafers. High areal energy (>10 µW h cm−2) and po...
Article
In recent years, there has been an increasing need for rechargeable energy-storage devices of many kinds. There are some applications for which energy density is important, whereas for others rate capability (high-power density) and prolonged durability are essential. Batteries address the need for high energy density, while electrochemical capacit...
Book
Electrochemical capacitors are electrochemical energy storage devices able to quickly deliver or store large quantities of energy. They have stimulated numerous innovations throughout the last 20 years and are now implemented in many fields. Supercapacitors Based on Carbon or Pseudocapacitive Materials provides the scientific basis for a better und...
Article
Full-text available
The development of high voltage spinel LiMn1.5Ni0.5O4 (LMNO) sputtered thin films on functional current collector was reported in the frame of this paper. We have firstly solved the technological issue of the PtSi phase which originates from the interdiffusion between silicon wafer and chromium/platinum current collector to form PtSi phase under an...
Article
Full-text available
The modification of carbide derived carbon (CDC) thin film electrodes with anthraquinone (AQ) molecules was demonstrated by using pulsed chronoamperometry, in 0.1 M NEt4BF4/ACN solution of AQ diazonium derivative. The functionalization of CDC electrodes was only possible when a critical pore size is reached: only 2 nm pore diameter CDC can be graft...
Article
The high power density of polymer exchange membrane fuel cells (PEMFCs) and hydrogen storage may be significantly hampered by the size and weight of the ancillaries needed to control air and hydrogen flow rates and humidity. In order to overcome these difficulties, a variety of research has been carried out on the development of hybrid systems base...
Article
We recently reported an impressive cycling stability (over 20,000 cycles) of titanium nitride (TiN) electrodes with high specific capacitance. It is anticipated that nitrogen (B-N) doping in the oxidized surface of TiN film plays a crucial role in charge storage mechanism and stability of this material. In this work, we offer an evidence on the eff...
Article
Full-text available
Over the past decade, interest in electrochemical capacitors as an energy-storage technology has increased enormously, spurring the development and evaluation of a large number of new materials and device configurations. This perspective article aims to propose guidelines by which new materials and devices should be evaluated, and how resulting dat...
Article
Electrochemical capacitors, so-called supercapacitors play an important role in energy storage and conversion systems. In the last decade, with the increasing volume of scientific activity and publications in this field, researchers have developed better tools to improve electrode materials. Although carbonaceous materials seem the most suitable fo...
Chapter
Pseudocapacitive materials involve rapid and reversible redox reactions responsible for charge storage. In pseudocapacitive materials, the electrostatic contribution of the double layer to the total capacitance is generally low due to limited electronic conductivity and/or a moderate surface area of the materials. This chapter focuses on electronic...
Chapter
This chapter discusses the manufacturing principles for the different types of hybrid and/or asymmetric devices in aqueous electrolytes and organic electrolytes, with examples illustrating the various designs and main trends for future devices. In the late 1990s, hybrid systems were proposed as an opportunity to increase the limited energy density...
Chapter
Carbon is the material of choice for supercapacitor electrodes (electrochemical double-layer capacitors [EDLCs]), because it meets three important requirements needed for active materials for electrochemical energy storage applications. They are: electrical conductivity; electrochemical stability; and high surface area that can be easily developed...
Chapter
This chapter focuses on conventional electrolytes based on organic solvents and/or ionic liquids, where noticeable progress has been made over the last few years. Organic electrolytes mainly used are acetonitrile (AN, CH3CN) or propylene carbonate (PC, C4H6O3) as a solvent with fluorinated salts such as tetraethylammonium tetrafluoroborate ((C2H5)4...
Article
Silicon nanowires were coated by a 1-5 nm thin alumina layer by Atomic Layer Deposition in order to replace poorly reproducible and unstable native silicon oxide by a highly conformal passivating alumina layer. The surface coating enabled probing the behavior of symmetric devices using such electrodes in EMI-TFSI electrolyte, allowing to attain a l...
Article
Here we report on the synthesis of binary transition metal nitride electrodes based on titanium vanadium nitride (TiVN) thin films. These films were deposited by a method compatible with micro-electronic processes which consists of DC co-sputtering of vanadium (V) and titanium (Ti) targets. TiVN films with different Ti/V ratio were deposited. A dep...
Article
Full-text available
Les microsupercondensateurs sont des microdispositifs de stockage réversible de l’énergie électrique constituant une alternative intéressante aux microbatteries en raison de leur puissance élevée et de leur durée de vie importante. La faible quantité d’énergie qu’ils peuvent emmagasiner reste cependant un point critique au déploiement de ces compos...
Chapter
The aim of this chapter is threefold. First of all, we will attempt to briefly highlight the differences between batteries and electrochemical capacitors (ECs), describe the general types of ECs (symmetric and asymmetric configurations), and present the electrochemical tools that are available to characterize these systems. Second, an EC is a compl...
Article
The push towards miniaturized electronics calls for the development of miniaturized energy-storage components that can enable sustained, autonomous operation of electronic devices for applications such as wearable gadgets and wireless sensor networks. Microsupercapacitors have been targeted as a viable route for this purpose, because, though storin...
Article
Full-text available
Nowadays, millimeter scale power sources are key devices for providing autonomy to smart, connected, and miniaturized sensors. However, until now, planar solid state microbatteries do not yet exhibit a sufficient surface energy density. In that context, architectured 3D microbatteries appear therefore to be a good solution to improve the material m...
Article
Highly dispersed crystalline/amorphous LiFePO4 (LFP) nanoparticles encapsulated within hollow-structured graphitic carbon were synthesized using an in situ ultracentrifugation process. Ultracentrifugation triggered an in situ sol-gel reaction that led to the formation of core-shell LFP simultaneously hybridized with fractured graphitic carbon. The...
Article
Vanadium nitride has displayed many interesting characteristics for its use as a pseudocapacitive electrode in an electrochemical capacitor, such as good electronic conductivity, good thermal stability, high density and high specific capacitance. Thin films of VN were prepared by D.C. reactive magnetron sputtering. The electrochemical stability of...
Article
Tailoring carbon based negative electrode by grafting electroactive 9,10-phenanthrenequinone molecules on porous carbon drastically improves the performance of a carbon/Ni(OH)2 hybrid electrochemical capacitor. The grafted-quinone moieties add a Faradaic contribution to the double layer capacitance of carbon leading to a significant increase of the...
Article
Spontaneous grafting of chloroanthraquinone (ClAQ) groups on Black Pearls carbon by reduction of the corresponding in-situ generated diazonium cations was successfully achieved. The presence of an halogen atom on the quinone molecule allowed the use of different spectroscopic characterization techniques to determine the accurate quinone content of...
Article
All-solid-state devices and thermal resistance to solder reflow are crucial issues with respect to micro-supercapacitors. While the latter issue can be addressed by using ionic liquids, the former shows promising results by employing the ionogel approach. The present study focuses on a novel formulation of ionogels - for use as solid state electrol...
Article
The electrochemical reversibility of lithium extraction from lithium rhenium oxide (Li5ReO6, LReO) has been studied using standard 1 mol L⁻¹ LiPF6 in EC/DMC electrolyte. An irreversible capacity of 410 mA h g⁻¹ was observed below 4.3 V vs. Li/Li⁺ (close to the total theoretical capacity of 423 mA h g⁻¹). Owing to this huge irreversible capacity, LR...
Article
Full-text available
Micro-supercapacitors are increasingly foreseen as future energy storage or power buffer solutions for small scale integration on-chip. However, widely used electrode materials or electrolytes often proved to be incompatible with microelectronics processes. Although being the material of choice for on-chip integration, nanostructured silicon electr...
Article
Herein, we report an improved method for the physical grafting of 1-nitropyrene (Pyr-NO2) onto highly graphitized carbon onion. This is achieved through a lowering of the onset potential of the pyrene polymerization via in situ reduction of the NO2 group. The additional redox activity pertaining to the reduced NO2 enables exceeding the faradaic cap...
Article
The use of non-stoichiometric lithium nickel oxide, being a part of the activated carbon positive electrode in lithium-ion capacitors, is presented as an alternative to the use of metallic lithium for graphite pre-lithiation. During the first cycle, lithium ions are irreversibly extracted from the Li0.65Ni1.35O2 host structure and intercalated into...
Article
Two commercial activated carbons, different from their texture, were grafted with electroactive molecules and tested for determining what texture is well-suited for the grafting. Microporous and mesoporous carbons, having approximately the same BET surface area, were selected. The electroactive molecule consists in a naphthalimide compound having a...
Article
In this work, we show a comparative study based on the effects of specific chemical functional groups (–OH, –NH2), grafted on Vulcan carbon (VC) with the incorporation of a specific polyoxometalate (POM), PMo12 (H3PMo12O40), to improve electrochemical performance. We observed a decrease in the specific surface area of the grafted matrices (VC-OH an...
Article
Full-text available
4-Carboxyphenyl groups are covalently grafted onto graphene oxide via diazonium chemistry for studying their role on the adsorption of iron oxide nanoparticles. The nanoparticles are deposited via a novel phase-transfer approach involving specific interactions at the interface between two immiscible solvents. The increased density and the homogeneo...