Centre Interuniversitaire de Recherche et d’Ingénierie des Matériaux

Electrochemical measurements can distinguish between different types of energy storage materials and their underlying mechanisms.

Electrochemical energy storage technology is based on devices capable of exhibiting high energy density (batteries) or high power density (electrochemical capacitors). There is a growing need, for current and near-future applications, where both high energy and high power densities are required in the same material. Pseudocapacitance, a faradaic process involving surface or near surface redox reactions, offers a means of achieving high energy density at high charge–discharge rates. Here, we focus on the pseudocapacitive properties of transition metal oxides. First, we introduce pseudocapacitance and describe its electrochemical features. Then, we review the most relevant pseudocapacitive materials in aqueous and non-aqueous electrolytes. The major challenges for pseudocapacitive materials along with a future outlook are detailed at the end.

The intercalation of ions into layered compounds has long been exploited in energy storage devices such as batteries and electrochemical capacitors. However, few host materials are known for ions much larger than lithium. We demonstrate the spontaneous intercalation of cations from aqueous salt solutions between two-dimensional (2D) Ti3C2 MXene layers. MXenes combine 2D conductive carbide layers with a hydrophilic, primarily hydroxyl-terminated surface. A variety of cations, including Na(+), K(+), NH4(+), Mg(2+), and Al(3+), can also be intercalated electrochemically, offering capacitance in excess of 300 farads per cubic centimeter (much higher than that of porous carbons). This study provides a basis for exploring a large family of 2D carbides and carbonitrides in electrochemical energy storage applications using single- and multivalent ions.

Carbon supercapacitors, which are energy storage devices that use ion adsorption on the surface of highly porous materials to store charge, have numerous advantages over other power-source technologies, but could realize further gains if their electrodes were properly optimized. Studying the effect of the pore size on capacitance could potentially improve performance by maximizing the electrode surface area accessible to electrolyte ions, but until recently, no studies had addressed the lower size limit of accessible pores. Using carbide-derived carbon, we generated pores with average sizes from 0.6 to 2.25 nanometer and studied double-layer capacitance in an organic electrolyte. The results challenge the long-held axiom that pores smaller than the size of solvated electrolyte ions are incapable of contributing to charge storage.

The research on electrochemical double layer capacitors (EDLC), also known as supercapacitors or ultracapacitors, is quickly expanding because their power delivery performance fills the gap between dielectric capacitors and traditional batteries. However, many fundamental questions, such as the relations between the pore size of carbon electrodes, ion size of the electrolyte, and the capacitance have not yet been fully answered. We show that the pore size leading to the maximum double-layer capacitance of a TiC-derived carbon electrode in a solvent-free ethyl-methylimmidazolium-bis(trifluoro-methane-sulfonyl)imide (EMI-TFSI) ionic liquid is roughly equal to the ion size (approximately 0.7 nm). The capacitance values of TiC-CDC produced at 500 degrees C are more than 160 F/g and 85 F/cm(3) at 60 degrees C, while standard activated carbons with larger pores and a broader pore size distribution present capacitance values lower than 100 F/g and 50 F/cm(3) in ionic liquids. A significant drop in capacitance has been observed in pores that were larger or smaller than the ion size by just an angstrom, suggesting that the pore size must be tuned with sub-angstrom accuracy when selecting a carbon/ion couple. This work suggests a general approach to EDLC design leading to the maximum energy density, which has been now proved for both solvated organic salts and solvent-free liquid electrolytes.

Exceptional performance claims for electrodes used in batteries and electrochemical capacitors often fail to hold up when all device components are included.

Ionic liquids offer a unique suite of properties that make them important candidates for a number of energy related applications. Cation–anion combinations that exhibit low volatility coupled with high electrochemical and thermal stability, as well as ionic conductivity, create the possibility of designing ideal electrolytes for batteries, super-capacitors, actuators, dye sensitised solar cells and thermo-electrochemical cells. In the field of water splitting to produce hydrogen they have been used to synthesize some of the best performing water oxidation catalysts and some members of the protic ionic liquid family co-catalyse an unusual, very high energy efficiency water oxidation process. As fuel cell electrolytes, the high proton conductivity of some of the protic ionic liquid family offers the potential of fuel cells operating in the optimum temperature region above 100 °C. Beyond electrochemical applications, the low vapour pressure of these liquids, along with their ability to offer tuneable functionality, also makes them ideal as CO2 absorbents for post-combustion CO2 capture. Similarly, the tuneable phase properties of the many members of this large family of salts are also allowing the creation of phase-change thermal energy storage materials having melting points tuned to the application. This perspective article provides an overview of these developing energy related applications of ionic liquids and offers some thoughts on the emerging challenges and opportunities.

Securing our energy future is the most important problem that humanity faces in this century. Burning fossil fuels is not sustainable, and wide use of renewable energy sources will require a drastically increased ability to store electrical energy. In the move toward an electrical economy, chemical (batteries) and capacitive energy storage (electrochemical capacitors or supercapacitors) devices are expected to play an important role. This Account summarizes research in the field of electrochemical capacitors conducted over the past decade. Overall, the combination of the right electrode materials with a proper electrolyte can successfully increase both the energy stored by the device and its power, but no perfect active material exists and no electrolyte suits every material and every performance goal. However, today, many materials are available, including porous activated, carbide-derived, and templated carbons with high surface areas and porosities that range from subnanometer to just a few nanometers. If the pore size is matched with the electrolyte ion size, those materials can provide high energy density. Exohedral nanoparticles, such as carbon nanotubes and onion-like carbon, can provide high power due to fast ion sorption/desorption on their outer surfaces. Because of its higher charge-discharge rates compared with activated carbons, graphene has attracted increasing attention, but graphene had not yet shown a higher volumetric capacitance than porous carbons. Although aqueous electrolytes, such as sodium sulfate, are the safest and least expensive, they have a limited voltage window. Organic electrolytes, such as solutions of [N(C2H5)4]BF4 in acetonitrile or propylene carbonate, are the most common in commercial devices. Researchers are increasingly interested in nonflammable ionic liquids. These liquids have low vapor pressures, which allow them to be used safely over a temperature range from -50 °C to at least 100 °C and over a larger voltage window, which results in a higher energy density than other electrolytes. In situ characterization techniques, such as nuclear magnetic resonance (NMR), small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS), and electrochemical quartz crystal microbalance (EQCM) have improved our understanding of the electrical double layer in confinement and desolvation of ions in narrow pores. Atomisitic and continuum modeling have verified and guided these experimental studies. The further development of materials and better understanding of charged solid-electrolyte interfaces should lead to wider use of capacitive energy storage at scales ranging from microelectronics to transportation and the electrical grid. Even with the many exciting results obtained using newer materials, such as graphene and nanotubes, the promising properties reported for new electrode materials do not directly extrapolate to improved device performance. Although thin films of nanoparticles may show a very high gravimetric power density and discharge rate, those characteristics will not scale up linearly with the thickness of the electrode.

Abstract Due to the tremendous importance of electrochemical energy storage, numerous new materials and electrode architectures for batteries and supercapacitors have emerged in recent years. Correctly characterizing these systems requires considerable time, effort, and experience to ensure proper metrics are reported. Many new nanomaterials show electrochemical behavior somewhere in between conventional double‐layer capacitor and battery electrode materials, making their characterization a non‐straightforward task. It is understandable that some researchers may be misinformed about how to rigorously characterize their materials and devices, which can result in inflation of their reported data. This is not uncommon considering the current state of the field nearly requires record breaking performance for publication in high‐impact journals. Incorrect characterization and data reporting misleads both the materials and device development communities, and it is the shared responsibility of the community to follow rigorous reporting methodologies to ensure published results are reliable to ensure constructive progress. This tutorial aims to clarify the main causes of inaccurate data reporting and to give examples of how researchers should proceed. The best practices for measuring and reporting metrics such as capacitance, capacity, coulombic and energy efficiencies, electrochemical impedance, and the energy and power densities of capacitive and pseudocapacitive materials are discussed.

Microbatteries with dimensions of tens to hundreds of micrometers that are produced by common microfabrication techniques are poised to provide integration of power sources onto electronic devices, but they still suffer from poor cycle lifetime, as well as power and temperature range of operation issues that are alleviated with the use of supercapacitors. There have been a few reports on thin-film and other micro-supercapacitors, but they are either too thin to provide sufficient energy or the technology is not scalable. By etching supercapacitor electrodes into conductive titanium carbide substrates, we demonstrate that monolithic carbon films lead to a volumetric capacity exceeding that of micro- and macroscale supercapacitors reported thus far, by a factor of 2. This study also provides the framework for integration of high-performance micro-supercapacitors onto a variety of devices.

Rechargeable non-lithium-ion (Na(+), K(+), Mg(2+), Ca(2+), and Al(3+)) batteries have attracted great attention as emerging low-cost and high energy-density technologies for large-scale renewable energy storage applications. However, the development of these batteries is hindered by the limited choice of high-performance electrode materials. In this work, MXene nanosheets, a class of two-dimensional transition-metal carbides, are predicted to serve as high-performing anodes for non-lithium-ion batteries by combined first-principles simulations and experimental measurements. Both O-terminated and bare MXenes are shown to be promising anode materials with high capacities and good rate capabilities, while bare MXenes show better performance. Our experiments clearly demonstrate the feasibility of Na- and K-ion intercalation into terminated MXenes. Moreover, stable multilayer adsorption is predicted for Mg and Al, which significantly increases their theoretical capacities. We also show that O-terminated MXenes can decompose into bare MXenes and metal oxides when in contact with Mg, Ca, or Al. Our results provide insight into metal ion storage mechanisms on two-dimensional materials and suggest a route to preparing bare MXene nanosheets.

Integration of electrochemical capacitors with silicon-based electronics is a major challenge, limiting energy storage on a chip. We describe a wafer-scale process for manufacturing strongly adhering carbide-derived carbon films and interdigitated micro-supercapacitors with embedded titanium carbide current collectors, fully compatible with current microfabrication and silicon-based device technology. Capacitance of those films reaches 410 farads per cubic centimeter/200 millifarads per square centimeter in aqueous electrolyte and 170 farads per cubic centimeter/85 millifarads per square centimeter in organic electrolyte. We also demonstrate preparation of self-supported, mechanically stable, micrometer-thick porous carbon films with a Young's modulus of 14.5 gigapascals, with the possibility of further transfer onto flexible substrates. These materials are interesting for applications in structural energy storage, tribology, and gas separation.

Recasting the double layer: The implicit assumption that electrochemical double layers are governed only by ion/electrode charge separation may be short-sighted and lead to a fundamental misunderstanding of the phenomenological response. This is shown in a study performed on ions confined in nanoporous carbon with pores smaller than the size of an ion surrounded by a solvation shell (see picture; TEA+=tetraethylammonium, AN=acetonitrile). Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z704894_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Since their commercialization Li-ion batteries have relied on the use of layered oxides (LiMO2) as positive electrodes. Over the years, via skilful chemical substitution their performances have drastically improved in terms of safety and capacity, which has nearly doubled (280 mAh/g) with the recent arrival of Li-rich NMC, i.e. layered LiCoO2 in which Co has been simultaneously replaced by Mn, Ni and Li. This review will aim to describe the chemical rationale which has led to this material evolution prior to focus on Li-rich NMC phases which are sources of excitement but challenges as well. The benefits of going back to fundamentals to rationalize and understand the new science at work with these Li-rich NMC phases will be stressed and illustrated by the discovery of a new reversible anionic redox process. Issues regarding voltage fade and limited rate capability which are plaguing their present utilization in commercial Li-ion cells will be addressed as well and solutions proposed. Owing to such advances, layered oxides which are over performing spinel or polyanionic-based compounds have a bright future.

The urgent need for efficient energy storage devices has stimulated a great deal of research on electrochemical double layer capacitors (EDLCs). This review aims at summarizing the recent progress in nanoporous carbons, as the most commonly used EDLC electrode materials in the field of capacitive energy storage, from the viewpoint of materials science and characterization techniques. We discuss the key advances in the fundamental understanding of the charge storage mechanism in nanoporous carbon-based electrodes, including the double layer formation in confined nanopores. Special attention will be also paid to the important development of advanced in situ analytical techniques as well as theoretical studies to better understand the carbon pore structure, electrolyte ion environment and ion fluxes in these confined pores. We also highlight the recent progress in advanced electrolytes for EDLCs. The better understanding of the charge storage mechanism of nanoporous carbon-based electrodes and the rational design of electrolytes should shed light on developing the next-generation of EDLCs.

The dc and ac conductivities of carbon nanotubes−polyepoxy composites have been investigated from 20 to 110 °C in the frequency range 10-2−106 Hz as a function of the conductive weight fraction p ranging from 0.04 to 2.5 wt %. The frequency dependence of the measured conductivity obeys the universal dynamic response (UDR): a dc plateau followed, above a critical frequency ωc, by the ωs power law with exponent s ∼ 0.6−1. The dc conductivity follows a percolation scaling law: σdc ∝ (p − pc)t with pc = 0.3 wt % and t = 1.4−1.8, according to the temperature. σdc reached 10-4 S/cm for 2.5 wt % CNTs content and increases with increasing temperature. Considering a biased random walk in three dimensions approach, we may explain the scaling law of ωc with p and its proportionality to σdc. The universality of ac conduction in carbon nanotubes−polymer composites is examined by the construction of master curves.

The global estimation of microplastic afloat in the ocean is only approximately 1% of annual global plastic inputs. This reflects fundamental knowledge gaps in the transformation, fragmentation, and fates of microplastics in the ocean. In order to better understand microplastic fragmentation we proceeded to a thorough physicochemical characterization of samples collected from the North Artlantic subtropical gyre during the sea campaign Expedition seventh Continent in May 2014. The results were confronted with a mathematical approach. The introduction of mass distribution in opposition to the size distribution commonly proposed in this area clarify the fragmentation pattern. The mathematical analysis of the mass distribution points out a lack of debris with mass lighter than 1 mg. Characterization by means of microscopy, microtomography, and infrared microscopy gives a better understanding of the behavior of microplastic at sea. Flat pieces of debris (2 to 5 mm in length) typically have one face that is more photodegraded (due to exposure to the sun) and the other with more biofilm, suggesting that they float in a preferred orientation. Smaller debris, with a cubic shape (below 2 mm), seems to roll at sea. All faces are evenly photodegraded and they are less colonized. The breakpoint in the mathematical model and the experimental observation around 2 mm leads to the conclusion that there is a discontinuity in the rate of fragmentation: we hypothesized that the smaller microplastics, the cubic ones mostly, are fragmented much faster than the parallelepipeds.

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Nickel nanoparticles of tunable shape have been synthesized in THF, in the presence of hexadecylamine (HDA) or trioctylphosphineoxide (TOPO), in mild conditions and characterized by HREM and SQUID measurements. The formation of nanorods is promoted by a high amine content in the reaction medium. In contrast to what is observed for TOPO-protected nickel particles, the saturation magnetization of HDA-capped nanoparticles is comparable to that of bulk nickel, which demonstrates that the coordination of an amine ligand does not alter the magnetic properties of nickel.

Abstract Assembly of 2D MXene sheets into a 3D macroscopic architecture is highly desirable to overcome the severe restacking problem of 2D MXene sheets and develop MXene‐based functional materials. However, unlike graphene, 3D MXene macroassembly directly from the individual 2D sheets is hard to achieve for the intrinsic property of MXene. Here a new gelation method is reported to prepare a 3D structured hydrogel from 2D MXene sheets that is assisted by graphene oxide and a suitable reductant. As a supercapacitor electrode, the hydrogel delivers a superb capacitance up to 370 F g −1 at 5 A g −1 , and more promisingly, demonstrates an exceptionally high rate performance with the capacitance of 165 F g −1 even at 1000 A g −1 . Moreover, using controllable drying processes, MXene hydrogels are transformed into different monoliths with structures ranging from a loosely organized porous aerogel to a dense solid. As a result, a 3D porous MXene aerogel shows excellent adsorption capacity to simultaneously remove various classes of organic liquids and heavy metal ions while the dense solid has excellent mechanical performance with a high Young's modulus and hardness.