Mathieu Morcrette

Mathieu Morcrette
Université de Picardie Jules Verne | UPJV · UFR of sciences

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146
Publications
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Publications

Publications (146)
Article
Aqueous electrolyte Li-ion–polysulphide batteries offer great promise due to the use of low-cost and abundant raw materials. Following up on our previous studies in which we explored a totally new practical battery chemistry coupling a well-known cathode material in Li-ion batteries (i.e. LiMn2O4) with a dissolved polysulphide anode, herein we aim...
Article
The synthesis and characterization of ionically conductive polymer films with high stretchability and good elasticity based on ionic semi-interpenetrating polymer networks (semi-IPNs) are discussed. Such innovative semi-IPN materials were prepared by radical copolymerization of ionic monomer, namely (N-[2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl]...
Article
Electrochemical energy storage devices such as batteries and supercapacitors are currently the subject of both fundamental and applied developments. This article presents the most significant breakthroughs in systems that are already on the market, in terms of materials, electrolytes, and improvement possibilities. Prospective systems are also pres...
Article
Macro-mesocellular carbonaceous foams bearing metallic (Pd or Au) nanoparticles have been synthesized and used to confine polysulfides at the cathode of Li-S batteries. We show that noble metal nanoparticles are interesting to tune the properties of cathode materials. On one hand, the surface chemistry of the metals enhances the polysulfides anchor...
Article
Size tuning for MoO2 nanoparticles is demonstrated for the first time over a wide range 2–100 nm, through a colloidal route into water. A nucleation-growth mechanism based on oriented attachment is evidenced to rationalize the impact of two simple synthetic levers: reactant ratio and temperature. The smallest non-aggregated crystalline MoO2 nanopar...
Article
Porous carbon foamswere prepared by pyrolysis of a phenolic resin by a dual template approach using silicamonoliths as hard templates and triblock copolymers as soft templating agents. A macroporosity of 50– 80% arose from the Si(HIPE) hard template, while the soft template generated micro- or meso-porosity according to the operating procedure. The...
Article
In spite of great research efforts on Li–S batteries in aprotic organic electrolytes, there have been very few studies showing the potential application of this system in aqueous electrolyte. Herein, we explore this option and report on a cheaper and safer new aqueous system coupling a well-known cathode material in Li-ion batteries (i.e. LiMn2O4)...
Article
Full-text available
Novel LiBH4–metal-loaded carbonaceous foams have been designed to trigger reversible hydrogen storage properties. The metallic nanoparticles favour preferential wetting of LiBH4 on their surface and subsequent nucleation and growth, a configuration in which borate formation is strongly minimized. A cooperative effect between lower boron oxidation a...
Article
A route towards carbon-MoO2 core-shell spheres has been developed, through hydrothermal decomposition of ascorbic acid combined with precipitation of MoO2 nanoparticles. In this one-pot and green process, carbon spheres originating from ascorbic acid act as seeds for the in situ deposition of a corona made of 30 nm molybdenum dioxide particles. The...
Article
Full-text available
Battery watch: UV/Vis spectrophotometry is demonstrated as a powerful analytical method for the in situ study of polysulfides. Through the interactions that occur between different chain-length polysulfide molecules and the UV/Vis radiation, quantitative and qualitative determination of the polysulfides formed during Li-S battery operation can be a...
Article
To improve the performance of the positive electrode in batteries, it is important to thoroughly characterize these materials during battery cycling, beyond just electrochemical characterization. Among the very few techniques available for operando studies, X-ray Absorption Spectroscopy (XAS) appears very powerful, with high spatial and time resolu...
Article
Well-defined macroporous V2O5–CNTs hybrid solid foams are synthesized in the form of monolith by a controlled bubbling process. For the first time, the solid phase results from the co-assembly of two different anisotropic nano-building blocks in the continuous phase of model foams whose bubble size and liquid fraction could be tuned. Their electroc...
Book
Lithium sulfur rechargeable batteries are foreseen to be used in electric vehicles in the near future. To enable their placement to the market we need to improve their reliability and cycling performance. This can be done by selective change of the chemical environment in the Li-S battery, including electrolyte (solvents and salts), different combi...
Article
Full-text available
Although promising improvements have been made in the field of Li-S rechargeable batteries, they are still far from reaching the market place due to several drawbacks. To combat the solubility of polysulphides, confinement approaches aiming to trap sulphur within the cathode side have been pursued, but success has been limited. Herein, we drastical...
Article
The precise characterization and structural analysis of positive electrodes for Li-ion batteries is essential for the development of long-life, safe and high-energy electrochemical systems. For this purpose X-Ray and neutron diffraction have proved to be essential tools in evaluating pristine powder materials (purity, cation ordering and distributi...
Article
A new MXene phase, Ti2C, obtained by aluminum extraction from Ti2AlC and exfoliation of the reaction product, was electrochemically studied vs. Lithium. Li-ions insertion into the 2-D structure was characterized by in situ XRD measurements. Additional electrochemical kinetic characterizations of Ti2C, using a cavity micro-electrode, showed that the...
Article
A new path for the design of safe and efficient, all-solid-state Li-ion batteries by spark plasma sintering (SPS) is considered. To reach a good electrochemical performance from such batteries, several parameters are investigated, such as the composite-electrode formulation (active material/electrolyte/carbon ratio) and the influence of the sinteri...
Article
By controlling and optimizing the formulation of a composite electrode and the sintering parameters (temperature, pressure), which affect compactness of both the electrolyte and the composite electrode, an efficient and safe monolithic solid-state Li-ion battery can be assembled in a one-step process by spark plasma sintering (SPS). On page 2140, R...
Article
Different Si clusters in Li12Si7 are resolved and their individual connectivities are analyzed by 29Si correlation NMR spectroscopy.
Article
Carbon coating of electrode materials is nowadays a major tool to improve the electronic percolation of the electrode. In this study, a self-generated carbon coating is described as a new way to deposit a regular thin layer of carbon on the surface of nanopartides. It relies on the soft decomposition of the nanopartides surface native ligands, cont...
Article
The use of the high energy Li-ion battery technology for emerging markets like electromobility requires precise appraisal of their safety levels in abuse conditions. Combustion tests were performed on commercial pouch cells by means of the Fire Propagation Apparatus also called Tewarson calorimeter in the EU, so far used to study flammability param...
Article
Structural signatures: The analysis of Si-Si and Si-Li connectivities by solid-state NMR spectroscopy allows the different types of silicon clusters to be discriminated in the model lithium silicide compound Li(12)Si(7) (see picture, Si clusters red and blue, Li ions gray). The results provide new NMR spectroscopic strategies with which to differen...
Article
Porous carbon foams were prepared by pyrolysis of phenolic resin from a dual-template approach using silica monoliths as hard templates and triblock copolymers as soft templating agents. Macroporosity of 50–80% arose from the Si(HIPE) hard template (the acronym “HIPE” refers to the high internal phase emulsion process), while the soft template gene...
Article
Li-S rechargeable batteries are attractive for electric transportation because of their low cost, environmentally friendliness, and superior energy density. However, the Li-S system has yet to conquer the marketplace, owing to its drawbacks, namely, soluble polysulfide formation. To tackle this issue, we present here a strategy based on the use of...
Article
Olivine LiFePO(4) is considered one of the most promising cathode materials for Li-ion batteries. A simple one-step, template-free, low-temperature solvothermal method is developed for the synthesis of urchinlike hierarchical mesocrystals of pristine LiFePO(4) as well as carbon-coated LiFePO(4) composites. Each urchinlike mesocrystal consists of Li...
Article
Bulk-type all-solid-state inorganic Li-ion batteries can be prepared in one step in few minutes using spark plasma sintering. The self-supported cells display thick composite electrodes of up to 800 μm, which offer high surface capacities of up to 10 mAh.cm-2. Such technology is safer than classical Li-ion batteries and offers good electrochemical...
Article
A modified 4-electrode Swagelok cell is proposed as an in situ analytical tool for the detection of soluble polysulphides in the electrolyte during lithium sulphur battery operation. Besides the standard Swagelok configuration, this cell has two additional perpendicular electrodes (wires) placed between two separators. Soluble polysulphides in the...
Article
Si/C/CMC composite for electrodes (Na-Carboxy-Methyl-Cellulose) appear today as the most promising strategy in view of substituting carbonaceous materials for silicon as negative active material in Li-ion batteries, hence the need to understand their reaction mechanism. By means of solid state Nuclear Magnetic Resonance spectroscopy, we confirmed t...
Article
The reversible Li-driven copper extrusion/insertion mechanism into Cu 2.33V4O11 electrode has been studied and a new ion-exchanged assisted electrochemical process was unravelled. This process, entails during the charging of "LixV4O11 + Cu0" composite electrodes vs. Li, the oxidation of Cu metal into copper ions that concomitantly exchanged for lit...
Article
Films of insertion compounds and solid state electrolytes have been synthesized in order to study their applications in the domain of electrochemical ion and gas sensors. Laser ablation was used to deposit lithium metal oxides (LiMO 2 where M is a transition metal Co or Mn). The chemical composition in the films has been studied by Rutherford Backs...
Article
Lithium ion batteries (LIBs) containing silicon negative electrodes have been the subject of much recent investigation, because of the extremely large gravimetric and volumetric capacities of silicon. The crystalline-to-amorphous phase transition that occurs on electrochemical Li insertion into crystalline Si, during the first discharge, hinders at...
Article
A high-throughput methodology combined with X-ray powder diffraction measurements was used to investigate the reactivity of the TetraThiaFulvalene TetraCarboxylic acid ((TTF-TC)H(4)) with divalent metals (M = Ni, Co) under various reaction conditions (stoichiometry, pH, temperature). Two new crystalline phases were identified and then studied by si...
Article
The reactivity of the redox-active tetracarboxylic acid derived from the tetrathiafulvalene (TTF-TC)H(4) with alkaline cations (K, Rb, Cs) is reported. The exploration of various experimental parameters (temperature, pH) led to the formation of four crystalline three-dimensional coordination polymers formulated M(2)(TTF-TC)H(2) (M = K, Rb, Cs), den...
Article
A new porous FeIII-based MOF, formulated Fe(OH)(BDC)·(dmf)x with x ≈ 1.1 and presenting the MIL-68 topology, was prepared by reaction of an iron(III) salt and terephthalic acid (H2BDC) in N,N′-dimethylformamide (dmf) under acidic conditions. The structure and properties of this solid were studied by means of X-ray diffraction, thermogravimetric ana...
Article
Full-text available
The possibility of using mechanical-fatigue life-prognostic methods for the life prediction of Li-ion batteries is evaluated. To this end, a physics-based model of a battery experiencing a single source of aging, i.e., the growth of a solid electrolyte interphase at the carbonaceous anode material, is employed as a surrogate battery. Dummy aging da...
Article
Microporous–macroporous carbononaceous monolith-type materials, prepared through a hard template method using silica as exo-templating matrices, have been impregnated with an etheric solution of LiBH4 to prepare LiBH4@carbon samples. It has been shown that the amorphous character of LiBH4 is largely favoured when developing the carbon microporosity...
Article
A lumped-parameter thermal model of a cylindrical LiFePO4/graphite lithium-ion battery is developed. Heat transfer coefficients and heat capacity are determined from simultaneous measurements of the surface temperature and the internal temperature of the battery while applying 2Hz current pulses of different magnitudes. For internal temperature mea...
Article
The present paper is in part a continuation of our recent work dealing with the fully reversible Li-driven Cu extrusion/injection of Cu in Cu2.33V4O11. The peculiar electrochemical property of such a compound was mainly ascribed to both structural considerations (presence of anchoring oxygen, giving flexibility to the [V4O11] layers) and electronic...
Article
We investigated the effect of inserting lithium into Ag2V4O11 (epsilon-SVO) on the structure, electronic properties and redox committed by combining in situ XRD measurements, ESR spectroscopy and 4 probes DC conductivity coupled with thermopower measurements. The electrochemical discharge occurs in three consecutive steps above 2 V (vs. Li+/Li). Th...
Article
Full-text available
A methodology for predicting the capacity loss of a battery under a complex current profile is provided. The prediction is based upon a set of elementary aging experiments, which are herein generated by a physics-based model featuring a surrogate battery, for which the source of aging is the growth of a solid-electrolyte interphase at the anode. Em...
Article
Using a hard exotemplate procedure, hierarchically structured carbonaceous foams have been designed, using silica monolith as inorganic template and phenolic resin as carbon precursor. The open cell carbonaceous monoliths exhibit specific surface areas from 500 to 800 m2.g-1, essentially based on microporosity and macropores ranging from 0.05 up to...
Article
A new electrochemical cell has been specially designed for operando experiments at synchrotron facilities both for X-ray diffraction and X-ray absorption. It allows the investigation of insertion materials under high current densities (up to 5C rate) and hence to study complex phenomena of structural and electronic changes out of equilibrium. The L...
Article
We investigated the effect of inserting lithium into Ag<sub>2</sub>V<sub>4</sub>O<sub>11</sub> (ε-SVO) on the structure, electronic properties and redox committed by combining in situ XRD measurements, ESR spectroscopy and 4 probes DC conductivity coupled with thermopower measurements. The electrochemical discharge occurs in three consecutive steps...
Article
Various Si/carbon/polymer composite electrodes were prepared to better understand the influence of the Si−polymer interactions on the stability of the Li−Si reaction and especially the superior performances of CMC-based (carboxy−methyl−cellulose) composites despite the large volume changes of the Si particles upon cycling. Via the modification of t...
Article
By using Si(HIPEs) as hard, exotemplating matrices, interconnected macro-/microporous carbon monolith-type materials with a surface area of around 600 m2 g−1 are synthesized and shaped. The carbonaceous foams exhibit a conductivity of 20 S cm−1, addressed with excellent mechanical properties (Young's modulus of 0.2 GPa and toughness of 13 J g−1, wh...
Article
X-ray absorption fine structure (XAFS) analysis of the Fe K-edge during lithium insertion and extraction into the metal organic framework material MIL-53 (FeIII(OH, F)bdc; bdc = benzene-1,4-dicarboxylate) reveals changes in local atomic environment about iron during the process. The average oxidation state of iron is reduced upon lithium insertion,...
Article
Density functional theory (DFT) calculations within the generalized gradient approximation (GGA) were performed to study phase transitions in lithium orthosalts Li3XO4 (X = P, As, V). The equilibrium crystal structure parameters and the total energies of the Li3XO4 polymorphs were calculated for the β- and γ-phases. The relative lattice stabilities...
Article
Among the metal-organic frameworks (MOFs), MIL-53(Fe) or FeIII(OH)0.8F0.2[O2C−C6H4−CO2] was the first ever reported member to reversibly insert Li+ electrochemically. A variety of electroactive sorbents has been investigated in an attempt to increase its electrochemical capacity vs Li+/Li0. Here, we describe the synthesis and characterization of a...
Article
Lithium-ion batteries (LIBs) containing silicon negative electrodes have been the subject of much recent investigation because of the extremely large gravimetric and volumetric capacity of silicon. The crystalline-to-amorphous phase transition that occurs on electrochemical Li insertion into crystalline Si, during the first discharge, hinders attem...
Article
Full-text available
An isothermal, multimodal, physics-based aging model for life prediction of Li-ion batteries is developed, for which a solvent decomposition reaction leading to the growth of a solid electrolyte interphase (SEI) at the carbonaceous anode material is considered as the source of capacity fade. The rate of SEI film growth depends on both solvent diffu...
Article
Full-text available
High-capacity Si-based electrodes could replace carbon-based electrodes in the next generation of Li-ion batteries. Although Si-based electrodes have large gravimetric capacities, they typically suffer from poor cyclability. One reason for the poor cyclability is large volume expansion associated with 3.75 mol of Li reacting with 1 mol of Si. A the...
Article
We demonstrate here the reversible electrochemical insertion of lithium into the hybrid porous solid FeIII(OH)0.8F0.2[O2C-C6H4-CO2]. Used as an electrode in Li-half cell, this material shows a reversible redox process around 3.0V vs. Li+/Li° exchanging 0.6Li per formula unit with interesting capacity retention and rate capability. Moreover, it reve...
Article
We report on the Li electrochemical reactivity of amorphous and crystalline VP2, synthesized by ball-milling and by 600°C heat treatment of a ball-milled sample, respectively. The amorphous sample can reversibly react with 3.5 Li per formula unit as compared to solely 2.5 for the crystalline one. However in both cases there is a rapid capacity deca...
Article
Full-text available
In the race for better Li-ion batteries, research on anode materials is very intensive as there is a strong desire to find alternatives to carbonaceous negative electrodes. A large part of these studies is devoted to alloying reactions, which have been known for more than thirty years but that have regained great interest by downsizing particle siz...
Article
Silicon-carbon composites consisting of Si particles embedded in a dense and non-porous carbon matrix are prepared by the pyrolysis of intimate mixtures of poly(vinyl chloride) (PVC) and Si powder at 900 degrees C under a flow of N(2). In contrast to bare micrometer-sized (1-10 mu m) and nanometer-sized (10-100 nm) Si powders, which show poor cycli...
Article
The reactivity of lithium with Cu2Sb was recently described to be governed by displacement reactions of Cu similar to those occurring in Cu2.33V4O11. In order to complement the earlier work of Fransson et al., we have revisited the electrochemical reactivity of Cu2Sb with Li. Through a different arsenal of characterization techniques, we have empha...
Article
Given the interest of silicates as potential electrode materials for lithium batteries, it is critical to fully understand the role that the inductive effect of the polyoxyanionic group, (XO4)n-, plays on the electrochemical performance of polyoxyanionic compounds. In this work we have combined experiments and first-principles methods to investigat...
Article
Lithiumbatterien: Als Elektrode in einer Lithium-Halbzelle zeigt das metall-organische Gerüst [LixFeIIxFeIII1−x(OH)0.8F0.2L] (L=O2CC6H4CO2) einen reversiblen Redoxprozess bei etwa 3.0 V gegen Li+/Li0, der durch eine interessante Kapazitätsretention und Strombelastbarkeit gekennzeichnet ist (siehe Spannungsprofil einer [LixFe(OH)0.8F0.2L]-Halbzelle;...
Article
There's more to LiFe: When used as an electrode in a lithium half cell, the metal-organic framework [LixFeIIxFe III1-x(OH)0.8-F0.2L] (L = O 2CC6H4CO2) shows a reversible redox process around 3.0 V versus Li+/ Li0 with interesting capacity retention and rate capability (see voltage profile for a [Li xFe(OH)0.8F0.2L] half cell; inset: representation...
Article
We show a continuous, in situ nuclear magnetic resonance (NMR) experiment on a lithium/graphite electrochemical cell. The objective is to study a commercial graphite currently used as negative electrodes in secondary lithium batteries. A plastic cell is made, with metallic lithium as the counter electrode and 1 mol dm−3 LiPF6/ethylene carbonate (EC...
Article
Several Li–Sn crystalline phases, i.e. Li2Sn5, LiSn, Li7Sn3, Li5Sn2, Li13Sn5, Li7Sn2 and Li22Sn5 were prepared by ball-milling and characterized by X-ray powder diffraction and 119Sn Mössbauer spectroscopy. The analysis of the Mössbauer hyperfine parameters, i.e. isomer shift (δ) and quadrupole splitting (Δ), made it possible to define two types of...
Article
We demonstrate here the reversible electrochemical insertion of lithium into the hybrid porous solid FeIII(OH)0.8F0.2[O2C-C6H4-CO2]. Used as an electrode in Li-half cell, this material shows a reversible redox process around 3.0V vs. Li+/Li° exchanging 0.6Li per formula unit with interesting capacity retention and rate capability. Moreover, it reve...
Article
Intermetallic phases Li-Sn were synthesized by ball-milling and characterized for their structures and electrochemical performances. All phases in Li-Sn binary phase diagram were identified by 119Sn Mössbauer spectroscopy, used as reference materials for the study of lithium insertion into tin-based electrode materials. The observed spectra show tw...
Article
The electrochemical reactivity of CuTi2S4 and CuCr2S4 spinel samples toward Li was studied over a wide range of voltages. Their electrochemical behavior can be decomposed into two steps. For less than two inserted lithium, we emphasized a Li-driven electrochemical displacement reaction that led to the extrusion of copper from lithium, leading to th...
Article
Light and flexible optical batteries based on plastic lithium-ion battery (PliON) technology have been recently proposed, and are able to modulate their reflection in the infrared range. We have focused our interest in the wavelength range 3–5 and 8–12μm range corresponding to two optical windows of light propagation in the atmosphere. The original...