Pseudocapacitance: From Fundamental Understanding to High Power Energy Storage 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.

Design of Carbon/Metal Oxide Hybrids for Electrochemical Energy Storage.

Next generation electrochemical energy storage materials that enable a combination of high specific energy, specific power, and cycling stability can be obtained by a hybridization approach. This involves electrode materials that contain carbon and metal oxide phases linked on a nanoscopic level and combine characteristics of supercapacitors and batteries. The combination of the components requires careful design to create synergistic effects for an increased electrochemical performance. Improved understanding of the role of carbon as a substrate has advanced the power handling and cycling stability of hybrid materials significantly in recent years. This Concept outlines different design strategies for the design of hybrid electrode materials: (1) the deposition of metal oxides on readily existing carbon substrates and (2) co-synthesizing both carbon and metal oxide phase during the synthesis procedure. The implications of carbon properties on the hybrid material's structure and performance will be assessed and the impact of the hybrid electrode architecture will be analyzed. The advantages and disadvantages of all approaches are highlighted and strategies to overcome the latter will be proposed.

Ordered Mesoporous Titania/Carbon Hybrid Monoliths for Lithium-ion Battery Anodes with High Areal and Volumetric Capacity.

Free-standing, binder-free, and conductive additive-free mesoporous titanium dioxide/carbon hybrid electrodes were prepared from co-assembly of a poly(isoprene)-block-poly(styrene)-block-poly(ethylene oxide) block copolymer and a titanium alkoxide. By tailoring an optimized morphology, we prepared macroscopic mechanically stable 300 µm thick monoliths that were directly employed as lithium-ion battery electrodes. High areal mass loading of up to 26.4 mg cm-2 and a high bulk density of 0.88 g cm-3 were obtained. This resulted in a highly increased volumetric capacity of 155 mAh cm-3 , compared to cast thin film electrodes. Further, the areal capacity of 4.5 mAh cm-2 represented a 9-fold increase compared to conventionally cast electrodes. These attractive performance metrics are related to the superior electrolyte transport and shortened diffusion lengths provided by the interconnected mesoporous nature of the monolith material, assuring superior rate handling, even at high cycling rates.

Hydronium Intercalation Enables High Rate in Hexagonal Molybdate Single Crystals.

Rapid proton transport in solid-hosts promotes a new chemistry in achieving high-rate Faradaic electrodes. Exploring the possibility of hydronium intercalation is essential for advancing proton-based charge storage. Nevertheless, this is yet to be revealed. Herein, a new host is reported of hexagonal molybdates, (A2 O)x ·MoO3 ·(H2 O)y (A = Na+ , NH4 + ), and hydronium (de)intercalation is demonstrated with experiments. Hexagonal molybdates show a battery-type initial reduction followed by intercalation pseudocapacitance. Fast rate of 200 C (40 A g-1 ) and long lifespan of 30 000 cycles are achieved in electrodes of monocrystals even over 200 µm. Solid-state nuclear magnetic resonance confirms hydronium intercalations, and operando measurements using electrochemical quartz crystal microbalance and synchrotron X-ray diffraction disclose distinct intercalation behaviours in different electrolyte concentrations. Remarkably, characterizations of the cycled electrodes show nearly identical structures and suggest equilibrium products are minimally influenced by the extent of proton solvation. These results offer new insights into proton electrochemistry and will advance correlated high-power batteries and beyond.

Structural and chemical characterization of MoO2/MoS2 triple-hybrid materials using electron microscopy in up to three dimensions.

This work presents the synthesis of MoO2/MoS2 core/shell nanoparticles within a carbon nanotube network and their detailed electron microscopy investigation in up to three dimensions. The triple-hybrid core/shell material was prepared by atomic layer deposition of molybdenum oxide onto carbon nanotube networks, followed by annealing in a sulfur-containing gas atmosphere. High-resolution transmission electron microscopy together with electron diffraction, supported by chemical analysis via energy dispersive X-ray and electron energy loss spectroscopy, gave proof of a MoO2 core covered by few layers of a MoS2 shell within an entangled network of carbon nanotubes. To gain further insights into this complex material, the analysis was completed with 3D electron tomography. By using Z-contrast imaging, distinct reconstruction of core and shell material was possible, enabling the analysis of the 3D structure of the material. These investigations showed imperfections in the nanoparticles which can impact material performance, i.e. for faradaic charge storage or electrocatalysis.

Binder-Free Hybrid Titanium-Niobium Oxide/Carbon Nanofiber Mats for Lithium-Ion Battery Electrodes.

Free-standing, binder-free, titanium-niobium oxide/carbon hybrid nanofibers are prepared for Li-ion battery applications. A one-pot synthesis offers a significant reduction of processing steps and avoids the use of environmentally unfriendly binder materials, making the approach highly sustainable. Tetragonal Nb2 O5 /C and monoclinic Ti2 Nb10 O29 /C hybrid nanofibers synthesized at 1000 °C displayed the highest electrochemical performance, with capacity values of 243 and 267 mAh g-1 , respectively, normalized to the electrode mass. At 5 A g-1 , the Nb2 O5 /C and Ti2 Nb10 O29 /C hybrid fibers maintained 78 % and 53 % of the initial capacity, respectively. The higher rate performance and stability of tetragonal Nb2 O5 compared to that of monoclinic Ti2 Nb10 O29 is related to the low energy barriers for Li+ transport in its crystal structure, with no phase transformation. The improved rate performance resulted from the excellent charge propagation in the continuous nanofiber network.

Atomic Layer-Deposited Molybdenum Oxide/Carbon Nanotube Hybrid Electrodes: The Influence of Crystal Structure on Lithium-Ion Capacitor Performance.

Merging of supercapacitors and batteries promises the creation of electrochemical energy storage devices that combine high specific energy, power, and cycling stability. For that purpose, lithium-ion capacitors (LICs) that store energy by lithiation reactions at the negative electrode and double-layer formation at the positive electrode are currently investigated. In this study, we explore the suitability of molybdenum oxide as a negative electrode material in LICs for the first time. Molybdenum oxide-carbon nanotube hybrid materials were synthesized via atomic layer deposition, and different crystal structures and morphologies were obtained by post-deposition annealing. These model materials are first structurally characterized and electrochemically evaluated in half-cells. Benchmarking in LIC full-cells revealed the influences of crystal structure, half-cell capacity, and rate handling on the actual device level performance metrics. The energy efficiency, specific energy, and power are mainly influenced by the overpotential and kinetics of the lithiation reaction during charging. Optimized LIC cells show a maximum specific energy of about 70 W·h·kg-1 and a high specific power of 4 kW·kg-1 at 34 W·h·kg-1. The longevity of the LIC cells is drastically increased without significantly reducing the energy by preventing a deep cell discharge, hindering the negative electrode from crossing its anodic potential limit.

Potential-Dependent, Switchable Ion Selectivity in Aqueous Media Using Titanium Disulfide.

The selective removal of ions by an electrochemical process is a promising approach to enable various water-treatment applications such as water softening or heavy-metal removal. Ion intercalation materials have been investigated for their intrinsic ability to prefer one specific ion over others, showing a preference for (small) monovalent ions over multivalent species. In this work, we present a fundamentally different approach: tunable ion selectivity not by modifying the electrode material, but by changing the operational voltage. We used titanium disulfide, which shows distinctly different potentials for the intercalation of different cations and formed binder-free composite electrodes with carbon nanotubes. Capitalizing on this potential difference, we demonstrated controllable cation selectivity by online monitoring the effluent stream during electrochemical operation by inductively coupled plasma optical emission spectrometry of aqueous 50 mm CsCl and MgCl2 . We obtained a molar selectivity of Mg2+ over Cs+ of 31 (strong Mg preference) in the potential range between -396 mV and -220 mV versus Ag/AgCl. By adjusting the operational potential window from -219 mV to +26 mV versus Ag/AgCl, Cs+ was preferred over Mg2+ by 1.7 times (Cs preference).