Energy Materials

Abstract Continuous and low-energy desalination technologies are in high demand to enable sustainable water remediation. Our work introduces a continuous desalination process based on the redox reaction of a dual-zinc electrode. The system consists of two zinc foils as redox electrodes with flowing ZnCl2 electrolyte, concentrated and diluted salt streams with three anion- and cation-exchange membranes (AEM and CEM) separated configuration (AEM|CEM|AEM). If a constant current is applied, the negative zinc electrode is oxidized, and electrons are released to the external circuit, whereas the positive zinc electrode is reduced, causing salt removal in the dilution stream. The results showed that brackish water can be directly desalted to 380.6 ppm during a continuous batch-mode process. The energy consumption can be as low as 35.30 kJ mol−1 at a current density of 0.25 mA cm−2, which is comparable to reverse osmosis. In addition, the dual-zinc electrode electrochemical desalination demonstrates excellent rate performance, reversibility, and batch cyclability through electrode exchange regeneration. Our research provides a route for continuous low-energy desalination based on metal redox mediators.

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.

Many metal sulfides present a layered structure with large interlayer space and a high theoretical capacity for lithium-ion battery applications. Compared to other transition metal dichalcogenides, vanadium sulfides remain little explored. Vanadium sulfides are commonly obtained by hydrothermal synthesis, which requires further post-processing and coating with binder and carbon additives. Here, we introduce a route to obtain free-standing vanadium sulfide fiber mats with in-built carbon. The combination of electrospinning and thermal sulfidation with H2S produces homogeneous vanadium sulfide particles embedded in carbon fibers that provide electrical conductivity and mechanical resistance for the electrode. The fibers were tested as a binder-free lithium-ion battery cathode within different potential ranges to evaluate insertion and conversion mechanisms and contributions to the overall capacity. Between 1.2 V and 3.5 V vs. Li/Li+, lithium intercalation provides a specific capacity up to 138 mAh∙g−1 at 0.01 A g−1 with good rate handling. When operating in a larger potential range between 0.1 V and 3.0 V vs. Li/Li+, the contribution by conversion reactions increases the capacity to 790 mAh∙g−1, but there is a fast capacity fading.

MAX phases are etched using an ionic liquid–water mixture to produce titanium carbide MXenes. The process avoids the use of any acid. Hydrolysis of the fluorine-containing ionic liquid leads to the selective removal of Al, while the ionic liquid is intercalated in-between the transition metal carbide layers.

Abstract The recent advances in chloride-ion capturing electrodes for capacitive deionization (CDI) are limited by the capacity, rate, and stability of desalination. This work introduces Ti3C2Tx/Ag synthesized via a facile oxidation-reduction method and then uses it as an anode for chloride-ion capture in CDI. Silver nanoparticles are formed successfully and uniformly distributed with the layered-structure of Ti3C2Tx. All Ti3C2Tx/Ag samples are hydrophilic, which is beneficial for water desalination. Ti3C2Tx/Ag samples with a low charge transfer resistance exhibit both pseudocapacitive and battery behaviors. Herein, the Ti3C2Tx/Ag electrode with a reaction time of 3 h exhibits excellent desalination performance with a capacity of 135 mg Cl− g−1 at 20 mA g−1 in a 10 × 10−3 m NaCl solution. Furthermore, low energy consumption of 0.42 kWh kg−1 Cl− and a desalination rate of 1.5 mg Cl− g−1 min−1 at 50 mA g−1 is achieved. The Ti3C2Tx/Ag system exhibits fast rate capability, high desalination capacity, low energy consumption, and excellent cyclability, which can be ascribed to the synergistic effect between the battery and pseudocapacitive behaviors of the Ti3C2Tx/Ag hybrid material. This work provides fundamental insight into the coupling of battery and pseudocapacitive behaviors during Cl− capture for electrochemical desalination.

Using electrodes with subnanometer pores and ionic liquid electrolytes can improve the charge storage capacity at the expense of the charging rate. The fundamental understanding of the charging dynamics of nanoporous electrodes can help to avoid compromising the power density. In this work, we performed molecular dynamics simulations to reveal the charging mechanism of subnanometer pores in ionic liquids. Different from the traditional view that a smaller pore results in slower charging, a non-monotonic relation is found between the charging rate and pore size, in which the charging process is accelerated in some subnanometer pores. Our analysis uncovers that the mechanism of the charging enhancement can be attributed to the transition of in-pore ion structure.

Electrodes based on alloying reactions for sodium-ion batteries (NIB) offer high specific capacity but require bespoken electrode material design to enable high performance stability. This work addresses that issue by systematically exploring the impact of carbon properties on antimony/carbon composite electrodes for NIBs. Since the Sb surface is covered by an insulating oxide layer, carbon additives are crucial for the percolation and electrochemical activity of Sb based anodes. Instead of using complex hybridization strategies, the ability of mechanical mixing to yield stable high-performance Sb/C sodium-ion battery (NIB) electrodes is shown. This is only possible by considering the physical, chemical, and structural features of the carbon phase. A comparison of carbon nanohorns, onion-like carbon, carbon black, and graphite as conductive additives is given in this work. The best performance is not triggered by the highest or lowest surface area, and not by highest or lowest heteroatom content, but by the best ability to homogenously distribute within the Sb matrix. The latter provides an optimum interaction between carbon and Sb and is best enabled by onion-like carbon. A remarkable rate performance is attained, electrode cracking caused by volume expansion is successfully prevented, and the homogeneity of the solid/electrolyte interphase is significantly improved as a result of it. With this composite electrode, a reversible capacity of 490 mA h g−1 at 0.1 A g−1 and even 300 mA g−1 at 8 A g−1 is obtained. Additionally, high stability with a capacity retention of 73% over 100 cycles is achieved at charge/discharge rates of 0.2 A g−1.

Aqueous iodine based electrochemical energy storage is considered a potential candidate to improve sustainability and performance of current battery and supercapacitor technology. It harnesses the redox activity of iodide, iodine, and polyiodide species in the confined geometry of nanoporous carbon electrodes. However, current descriptions of the electrochemical reaction mechanism to interconvert these species are elusive. Here we show that electrochemical oxidation of iodide in nanoporous carbons forms persistent solid iodine deposits. Confinement slows down dissolution into triiodide and pentaiodide, responsible for otherwise significant self-discharge via shuttling. The main tools for these insights are in situ Raman spectroscopy and in situ small and wide-angle X-ray scattering (in situ SAXS/WAXS). In situ Raman confirms the reversible formation of triiodide and pentaiodide. In situ SAXS/WAXS indicates remarkable amounts of solid iodine deposited in the carbon nanopores. Combined with stochastic modeling, in situ SAXS allows quantifying the solid iodine volume fraction and visualizing the iodine structure on 3D lattice models at the sub-nanometer scale. Based on the derived mechanism, we demonstrate strategies for improved iodine pore filling capacity and prevention of self-discharge, applicable to hybrid supercapacitors and batteries.

The freshwater scarcity and increasing energy demand are two challenging global issues. Herein, we propose a new route for desalination, self-sustained visible-light-driven electrochemical redox desalination. We propose a novel device architecture involving internal integration of a quasi-solid-state dye-sensitized solar cell and continuous redox-flow desalination units with a bifunctional platinized-graphite-paper electrode. Both the solar cell and redox-flow desalination units are integrated using the bifunctional electrode with one side facing the solar cell operating as a positive electrode and the other side facing the redox-flow desalination unit operating as a negative electrode. The solar cell contains a gel-based tri-iodide/iodide redox couple sandwiched between an N719 dye-modified photoanode and cathode. In contrast, the redox-flow desalination consists of re-circulating ferro/ferricyanide redox couple sandwiched between the anode and cathode with two salt streams located between these electrodes. The performances of bifunctional electrodes in both redox couples were thoroughly investigated by electrochemical characterization. The brackish feed can be continuously desalted to the freshwater level by utilizing visible light illumination. As a device, this architecture combines energy conversion and water desalination. This concept bypasses the need for electrical energy consumption for desalination, which provides a novel structural design using photodesalination to facilitate the development of self-sustained solar desalination technologies.

This study demonstrates the hybridization of Li4Ti5O12 (LTO) with different types of carbon onions synthesized from nanodiamonds. The carbon onions mixed with a Li4Ti5Ox precursor for sol–gel synthesis. These hybrid materials are tested as anodes for both lithium-ion battery (LIB) and sodium-ion battery (SIB). Electrochemical characterization for LIB application is carried out using 1 m LiPF6 in a 1:1 (by volume) ethylene carbonate and dimethyl carbonate as the electrolyte. For lithium-ion intercalation, LTO hybridized with carbon onions from the inert-gas route achieves an excellent electrochemical performance of 188 mAh g−1 at 10 mA g−1, which maintains 100 mAh g−1 at 1 A g−1 and has a cycling stability of 96% of initial capacity after 400 cycles, thereby outperforming both neat LTO and LTO with onions obtained via vacuum treatment. The performance of the best-performing hybrid material (LTO with carbon onions from argon annealing) in an SIB is tested, using 1 m NaClO4 in ethylene/dimethyl/fluoroethylene carbonate (19:19:2 by mass) as the electrolyte. A maximum capacity of 102 mAh g−1 for the SIB system is obtained, with a capacity retention of 96% after 500 cycles.