Chem Commun (Camb)
May 2023
Water plays an essential role in the development of society. However, the worldwide supply of drinking water is becoming a challenge that needs to be addressed in the future. In this review we focus on new electrochemical technologies based on the concept of desalination batteries (DBs) and which feature different desalination approaches based on battery-like technologies reported to date.
View Article and Find Full Text PDFDifferent strategies can be used to acquire dynamic impedance spectra during a cyclic voltammetry experiment. The spectra are then analyzed by fitting them with a model using a weighted non-linear least-squares minimization algorithm. The choice of the weighting factors is not trivial and influences the value of the extracted parameters.
View Article and Find Full Text PDFThe ever-increasing amount of batteries used in today's society has led to an increase in the demand of lithium in the last few decades. While mining resources of this element have been steadily exploited and are rapidly depleting, water resources constitute an interesting reservoir just out of reach of current technologies. Several techniques are being explored and novel materials engineered.
View Article and Find Full Text PDFIonic liquid electrolytes (ILEs) have become popular in various advanced Li-ion battery chemistries because of their high electrochemical and thermal stability and low volatility. However, because of their relatively high viscosity and poor Li diffusion, it is thought large concentration gradients form, reducing their rate capability. Herein, we utilize operando Raman microspectroscopy to visualize ILE concentration gradients for the first time.
View Article and Find Full Text PDFAqueous zinc-ion batteries are realistic candidates as stationary storage systems for power-grid applications. However, to accelerate their commercialization, some important challenges must be specifically tackled, and appropriate experimental practices need to be embraced to align the academic research efforts with the realistic industrial working conditions for stationary storage. Within this commentary article, both the open challenges and the good experimental practices are discussed in relation to their impact on the future development of the aqueous Zn-ion technology.
View Article and Find Full Text PDFKnowledge of electrolyte transport and thermodynamic properties in Li-ion and beyond Li-ion technologies is vital for their continued development and success. Here, we present a method for fully characterising electrolyte systems. By measuring the electrolyte concentration gradient over time via operando Raman microspectroscopy, in tandem with potentiostatic electrochemical impedance spectroscopy, the Fickian "apparent" diffusion coefficient, transference number, thermodynamic factor, ionic conductivity and resistance of charge-transfer were quantified within a single experimental setup.
View Article and Find Full Text PDFThe spinel LiMnO (LMO) is a promising cathode material for rechargeable Li-ion batteries due to its excellent properties, including cost effectiveness, eco-friendliness, high energy density, and rate capability. The commercial application of LiMnO is limited by its fast capacity fading during cycling, which lowers the electrochemical performance. In the present work, phase-pure and crystalline LiMnO spinel in the nanoscale were synthesized using single flame spray pyrolysis via screening 16 different precursor-solvent combinations.
View Article and Find Full Text PDFDynamic impedance spectroscopy is one of the most powerful techniques in the qualitative and quantitative mechanistic studies of electrochemical systems, as it allows for time-resolved investigation and dissection of various physicochemical processes occurring at different time scales. However, due to high-frequency artefacts connected to the non-ideal behaviour of the instrumental setup, dynamic impedance spectra can lead to wrong interpretation and/or extraction of wrong kinetic parameters. These artefacts arise from the non-ideal behaviour of the voltage and current amplifier (I/E converters) and stray capacitance.
View Article and Find Full Text PDFThe efficient production of energy from low-temperature heat sources (below 100 °C) would open the doors to the exploitation of a huge amount of heat sources such as solar, geothermal, and industrial waste heat. Thermal regenerable redox-flow batteries (TRBs) are flow batteries that store energy in concentration cells that can be recharged by distillation at temperature <100 °C, exploiting low-temperature heat sources. Using a single membrane cell setup and a suitable redox couple (LiBr/Br ), a TRB has been developed that is able to store a maximum volumetric energy of 25.
View Article and Find Full Text PDFDue to the ubiquitous presence of lithium-ion batteries in portable applications, and their implementation in the transportation and large-scale energy sectors, the future cost and availability of lithium is currently under debate. Lithium demand is expected to grow in the near future, up to 900 ktons per year in 2025. Lithium utilization would depend on a strong increase in production.
View Article and Find Full Text PDFThe mechanism of the hydrogen evolution reaction, although intensively studied for more than a century, remains a fundamental scientific challenge. Many important questions are still open, making it elusive to establish rational principles for electrocatalyst design. In this work, a comprehensive investigation was conducted to identify which dynamic phenomena at the electrified interface are prerequisite for the formation of molecular hydrogen.
View Article and Find Full Text PDFDynamic multi-frequency analysis (DMFA) is capable of acquiring high-quality frequency response of electrochemical systems under non-stationary conditions in a broad range of frequencies. In this work, we used DMFA to study the kinetics of (de-)intercalation of univalent cations (Na and K) in thin films of nickel hexacyanoferrate (NiHCF) during cyclic voltammetry. For this system, the classic stationary electrochemical impedance spectroscopy fails due to the instability of the oxidized form of NiHCF.
View Article and Find Full Text PDFThe structural changes of copper hexacyanoferrate (CuHCF), a Prussian blue analogue, which occur when used as a cathode in an aqueous Zn-ion battery, are investigated using electron microscopy techniques. The evolution of Zn Cu HCF phases possessing wire and cubic morphologies from initial CuHCF nanoparticles are monitored after hundreds of cycles. Irreversible introduction of Zn ions to CuHCF is revealed locally using scanning transmission electron microscopy.
View Article and Find Full Text PDFACS Appl Mater Interfaces
March 2019
Composites consisting of garnet-type LiLaZrO (LLZO) ceramic particles dispersed in a solid polymer electrolyte based on poly(ethylene oxide) (PEO) have recently been investigated as a possible electrolyte material in all solid state Li ion batteries. The interface between the two materials, that is, LLZO/PEO, is of special interest for the transport of lithium ions in the composite. For obtaining the desired high ionic conductivity, Li ions have to pass easily across this interface.
View Article and Find Full Text PDFThe crystal orientation and morphology of sputtered LiMnO thin films is strongly affected by the current collector. By substituting Pt with Au, it is possible to observe in the x-ray diffraction pattern of LiMnO a change in the preferential orientation of the grains from (111) to (400). In addition, LiMnO thin films deposited on Au show a higher porosity than films deposited on Pt.
View Article and Find Full Text PDFHigh voltage operating active materials are among the most promising components for positive electrodes of future high energy lithium-ion batteries. However, the operating potential range of such materials often exceeds anodically the thermodynamic stability window of the electrolyte. A surface layer is therefore formed, which is supposed to be one of the reasons for the high irreversible charge loss of these electrodes.
View Article and Find Full Text PDFReversible mixed-ion intercalation in nonselective host structures has promising applications in desalination, mixed-ion batteries, wastewater treatment, and lithium recovery through electrochemical ion pumping. One class of host compound that possesses many of the requirements needed for such applications (cost effectiveness, fast ion kinetics, and stability in an aqueous medium) includes the Prussian blue derivatives. Herein, the fundamental process of intercalation of multiple cations is studied at the thermodynamic level by means of galvanostatic cycling.
View Article and Find Full Text PDFThe high (de)lithiation potential of TiO (ca. 1.7 V vs Li/Li in 1 M Li) decreases the voltage and, thus, the energy density of a corresponding Li-ion battery.
View Article and Find Full Text PDFUnderstanding the gas evolution in batteries, caused by decomposition of the electrolyte, is of fundamental importance for improving the long-time performances and cycle life of the battery systems. In general, this phenomenon causes simultaneously an irreversible energy and charge loss, as well as an increase of the internal resistance. Here, we introduce a new cell design capable of performing electrochemical impedance spectroscopy (EIS) and differential electrochemical mass spectroscopy (DEMS) with high resolution.
View Article and Find Full Text PDFCurrently, lithium carbonate is mainly produced through evaporation of lithium-rich brines, which are located in South American countries such as Bolivia, Chile, and Argentina. The most commonly used process, the lime-soda evaporation, requires a long time and several purification steps, which produces a considerable amount of chemical waste. Recently, several alternative electrochemical methods, based on LiFePO4 as a selective lithium capturing electrode and differing for the reaction at the counter electrode, have been proposed.
View Article and Find Full Text PDFHighly reproducible and fast potential-assisted immobilization of single-stranded (ss)DNA on gold surfaces is achieved by applying a pulse-type potential modulation. The desired DNA coverage can be obtained in a highly reproducible way within minutes. Understanding the underlying processes occurring during potential-assisted ssDNA immobilization is crucial.
View Article and Find Full Text PDFACS Appl Mater Interfaces
October 2015
The solid electrolyte interphase (SEI) film formed at the surface of negative electrodes strongly affects the performance of a Li-ion battery. The mechanical properties of the SEI are of special importance for Si electrodes due to the large volumetric changes of Si upon (de)insertion of Li ions. This manuscript reports the careful determination of the Young's modulus of the SEI formed on a sputtered Si electrode using wet atomic force microscopy (AFM)-nanoindentation.
View Article and Find Full Text PDFIn situ and operando techniques can play important roles in the development of better performing photoelectrodes, photocatalysts, and electrocatalysts by helping to elucidate crucial intermediates and mechanistic steps. The development of high throughput screening methods has also accelerated the evaluation of relevant photoelectrochemical and electrochemical properties for new solar fuel materials. In this chapter, several in situ and high throughput characterization tools are discussed in detail along with their impact on our understanding of solar fuel materials.
View Article and Find Full Text PDFA new zinc-ion battery based on copper hexacyanoferrate and zinc foil in a 20 mM solution of zinc sulfate, which is a nontoxic and noncorrosive electrolyte, at pH 6 is reported. The voltage of this novel battery system is as high as 1.73 V.
View Article and Find Full Text PDFThe demand for lithium will increase in the near future to 713,000 tonnes per year. Although lake brines contribute to 80% of the production, existing methods for purification of lithium from this source are expensive, slow, and inefficient. A novel electrochemical process with low energy consumption and the ability to increase the purity of a brine solution to close to 98% with a single-stage galvanostatic cycle is presented.
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