Pseudocapacitors based on redox-active materials have relatively high energy density but suffer from low power capability. Here the authors report that two-dimensional transition metal carbides exhibit high gravimetric, volumetric and areal capacitance values at high char…

https://hal.archives-ouvertes.fr/hal-02007475/document

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

A strategy to prepare flexible and conductive MXene/graphene (reduced graphene oxide, rGO) supercapacitor electrodes by using electrostatic self-assembly between positively charged rGO modified with poly(diallyldimethylammonium chloride) and negatively charged titanium carbide MXene nanosheets is presented. After electrostatic assembly, rGO nanosheets are inserted in-between MXene layers. As a result, the self-restacking of MXene nanosheets is effectively prevented, leading to a considerably increased interlayer spacing. Accelerated diffusion of electrolyte ions enables more electroactive sites to become accessible. The freestanding MXene/rGO-5 wt% electrode displays a volumetric capacitance of 1040 F cm−3 at a scan rate of 2 mV s−1 , an impressive rate capability with 61% capacitance retention at 1 V s−1 and long cycle life. Moreover, the fabricated binder-free symmetric supercapacitor shows an ultrahigh volumetric energy density of 32.6 Wh L−1, which is among the highest values reported for carbon and MXene based materials in aqueous electrolytes. This work provides fundamental insight into the effect of interlayer spacing on the electrochemical performance of 2D hybrid materials and sheds light on the design of next-generation flexible, portable and highly integrated supercapacitors with high volumetric and rate performances.

Flexible MXene/Graphene Films for Ultrafast Supercapacitors with Outstanding Volumetric Capacitance

Batteries and supercapacitors serve as the basis for electrochemical energy-storage devices. Although both rely on electrochemical processes, their charge-storage mechanisms are dissimilar, giving rise to different energy and power densities. Pseudocapacitive materials store charge through battery-like redox reactions but at fast rates comparable to those of electrochemical double-layer capacitors; these materials, therefore, offer a pathway for achieving both high energy and high power densities. Materials that combine these properties are in demand for the realization of fast-charging electrochemical energy-storage devices capable of delivering high power for long periods of time. In this Review, we describe the fundamental electrochemical properties of pseudocapacitive materials, with emphasis on kinetic processes and distinctions between battery and pseudocapacitive materials. In addition, we discuss the various types of pseudocapacitive materials, highlighting the differences between intrinsic and extrinsic materials; assess device applications; and consider the future prospects for the field. Pseudocapacitive materials can bridge the gap between high-energy-density battery materials and high-power-density electrochemical capacitor materials. In this Review, we examine the electrochemistry and physical signatures of pseudocapacitive charge-storage processes and discuss existing pseudocapacitive materials.

Achieving high energy density and high power density with pseudocapacitive materials

There is an urgent global need for electrochemical energy storage that includes materials that can provide simultaneous high power and high energy density One strategy to achieve this goal is with pseudocapacitive materials that take advantage of reversible surface or near-surface Faradaic reactions to store charge This allows them to surpass the capacity limitations of electrical double-layer capacitors and the mass transfer limitations of batteries The past decade has seen tremendous growth in the understanding of pseudocapacitance as well as materials that exhibit this phenomenon The purpose of this Review is to examine the fundamental development of the concept of pseudocapacitance and how it came to prominence in electrochemical energy storage as well as to describe new classes of materials whose electrochemical energy storage behavior can be described as pseudocapacitive

Pseudocapacitance: From Fundamental Understanding to High Power Energy Storage Materials

2D transition-metal carbides and nitrides, known as MXenes, have displayed promising properties in numerous applications, such as energy storage, electromagnetic interference shielding, and catalysis. Titanium carbide MXene (Ti3 C2 Tx ), in particular, has shown significant energy-storage capability. However, previously, only micrometer-thick, nontransparent films were studied. Here, highly transparent and conductive Ti3 C2 Tx films and their application as transparent, solid-state supercapacitors are reported. Transparent films are fabricated via spin-casting of Ti3 C2 Tx nanosheet colloidal solutions, followed by vacuum annealing at 200 °C. Films with transmittance of 93% (≈4 nm) and 29% (≈88 nm) demonstrate DC conductivity of ≈5736 and ≈9880 S cm-1 , respectively. Such highly transparent, conductive Ti3 C2 Tx films display impressive volumetric capacitance (676 F cm-3 ) combined with fast response. Transparent solid-state, asymmetric supercapacitors (72% transmittance) based on Ti3 C2 Tx and single-walled carbon nanotube (SWCNT) films are also fabricated. These electrodes exhibit high capacitance (1.6 mF cm-2 ) and energy density (0.05 µW h cm-2 ), and long lifetime (no capacitance decay over 20 000 cycles), exceeding that of graphene or SWCNT-based transparent supercapacitor devices. Collectively, the Ti3 C2 Tx films are among the state-of-the-art for future transparent, conductive, capacitive electrodes, and translate into technologically viable devices for next-generation wearable, portable electronics.

Transparent, Flexible, and Conductive 2D Titanium Carbide (MXene) Films with High Volumetric Capacitance.

MXenes represent an emerging family of conductive two-dimensional materials. Their representative, Ti3C2Tx, has been recognized as an outstanding member in the field of electrochemical energy storage. However, an in-depth understanding of fundamental processes responsible for the superior capacitance of Ti3C2Tx MXene in acidic electrolytes is lacking. Here, to understand the mechanism of capacitance in Ti3C2Tx MXene, we studied electrochemically the charge/discharge processes of Ti3C2Tx electrodes in sulfate ion-containing aqueous electrolytes with three different cations, coupled with in situ Raman spectroscopy. It is demonstrated that hydronium in the H2SO4 electrolyte bonds with the terminal O in the negative electrode upon discharging while debonding occurs upon charging. Correspondingly, the reversible bonding/debonding changes the valence state of Ti element in the MXene, giving rise to the pseudocapacitance in the acidic electrolyte. In stark contrast, only electric double layer capacitance is reco...

High-Capacitance Mechanism for Ti3C2Tx MXene by in Situ Electrochemical Raman Spectroscopy Investigation


 It’s critical to quantitatively investigate the thermal characteristics of single overcharged lithium-ion batteries to realize security alert before thermal runaway occurs. In this work, various (LiCoO2 + LiMn2O4)/graphite soft pack cells overcharged under different cut-off voltages, temperatures and C-rates are tested electrochemically to calculate the heat generation rate and distinguish the dominating heat resource. The results show that overcharged cells with higher cut-off voltage, overcharge temperature and the lower overcharge C-rate exhibit higher heat generation and temperature rise rate as well as poorer state of healthy. Among nonexplosive tested cells, the cell overcharged to 4.8 V at 0.1 C rate and 40°C exhibits the highest heat generation and temperature rise rates of 9.17 W·L-1 and 4.60 °C·h-1 during 1 C charging at 25°C. For overcharged cells, lithium plating, increased resistance and gas generation are observed, which are the reason for the accelerated total heat generation rate compared to baseline cells. Comparing with reversible heat, the irreversible heat resulting from diffusion overpotential and the sum of ohmic and charge transfer overpotential is dominating for overcharged cells working under high current. It’s recommended to comprehensively monitor the temperature change of each cell of battery pack.

Heat Generation and Temperature Rise Characteristics of Single Overcharged Lithium-Ion Batteries

Recently, the natural heterostructure of (PbSe)5-(Bi2Se3)6 has been theoretically predicted and experimentally confirmed as a topological insulator. In this work, we induce superconductivity in (PbSe)5(Bi2Se3)6 by implementing high pressures. As the pressure increases up to 10 GPa, superconductivity with a critical temperature (Tc) ~ 4.6 K suddenly appears, which is followed by an abrupt decrease. Remarkably, upon further compression above 30 GPa, a new superconducting state arises, where pressure raises the Tc to an unsaturated 6.0 K within the limit of our research. Combining X-ray diffraction and Raman spectroscopy, we suggest that the emergence of the two distinct superconducting states occurs concurrently with the pressure-induced structural transition in this topological heterostructure (PbSe)5(Bi2Se3)6. 

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Pressure-induced superconductivity in topological heterostructure (PbSe)5(Bi2Se3)6

Development of a combustion reaction model for lubricant synthetic base oil by experimental and numerical methods

The reporter-spacer-receptor (RSR) approach is prevalent to develop molecular turn-on sensors. However, the fluorescent RSR sensors barely operate in solid state, which hinders their fabrication into devices for practical applications. Herein, we present a novel strategy to achieve solid-state luminescence turn-on sensing by assembling RSR architectures within MOF frameworks. Unlike the regular RSR systems, the framework-confined fluorophore and receptor are well arranged and separated even in the solid state. This concept is illustrated by a multicomponent MOF (Fc@NU-1000), which contains organic linkers with a highly luminescent pyrene core as the reporter, Zr6 nodes with unsaturated sites as the receptor, and the incorporated Fc molecules as the quencher. The separate incorporation of pyrene core and Fc in the multicomponent MOF favors an efficient pseudointramolecular photoinduced electron transfer (PET) process, resulting in significant luminescence quenching. Interestingly, such PET process can be blocked via the quencher displacement initiated by the phosphate analyte, therefore recovering the solid-state luminescence of MOF microcrystals. We found that Fc@NU-1000 is shown as a sensitive solid-state luminescence turn-on probe for phosphate with the naked-eye response at a low content. What's more, this study is the first example of confining a quencher displacement-based RSR system in the MOF framework for solid-state luminescence turn-on sensing, thus also providing new opportunities for MOF materials to develop luminescence turn-on sensors.

Shihao Zhu

Papers

High-Capacitance Mechanism for Ti3C2Tx MXene by in Situ Electrochemical Raman Spectroscopy Investigation

Heat Generation and Temperature Rise Characteristics of Single Overcharged Lithium-Ion Batteries

Pressure-induced superconductivity in topological heterostructure (PbSe)5(Bi2Se3)6

Development of a combustion reaction model for lubricant synthetic base oil by experimental and numerical methods

Solid-State Luminescence Turn-On Sensing Using MOF-Confined Reporter-Spacer-Receptor Architectures Facilitated by Quencher Displacement.