Effect of [Na+]/[Li+] concentration ratios in brines on lithium carbonate production through membrane electrolysis.

Lithium is a fundamental raw material for the production of rechargeable batteries. The technology currently in use for lithium salts recovery from continental brines entails the evaporation of huge water volumes in desert environments. It also requires that the native brines reside for not less than a year in open air ponds, and is only applicable to selected compositions, not allowing its application to more diluted brines such as those geothermally sourced or waters produced from the oil industry. We have proposed an alternative technology based on membrane electrolysis. In three consecutive water electrolyzers, fitted alternately with anion and cation permselective membranes, we have shown, at proof-of-concept level, that it is possible to sequentially recover lithium carbonate and several by-products, including magnesium and calcium hydroxide, sodium bicarbonate, H2 and HCl. The big challenge is to bring this technology closer to practical implementation. Thus, the issue is how to apply relatively well-known electrochemical technology principles to large volumes and to a highly complex and saline broth. We have studied the application of this new methodology to ternary mixtures (NaCl, LiCl and KCl) with constant LiCl and KCl composition and increasing NaCl content. Results showed very similar behaviour for systems containing [Na+]/[Li+] concentration ratios ranging from 1.24 to 4.80. The voltage developed between the anode and cathode is almost the same in all systems at roughly 3.5 V when a constant current density of 50 A m-2 is applied. The three monovalent cations migrate with different rates across the cation exchange membrane, with Li+ being the most sluggish and thus crystallization of Li2CO3 only occurs close to completion of the electrolysis. The dimensionless concentration profiles are almost indistinguishable despite the changes in total salinity. The solids crystallized from different feeds showed higher Na+ and K+ contents as the initial Na+ concentration was increased. However, solids with over 99.9% purity in Li2CO3 could be obtained after a simple re-suspension treatment in hot water. The electrochemical energy consumption greatly increases with higher Na+ concentrations, and the amount of fresh water that can be recovered is diminished.

Purposely Designed Hierarchical Porous Electrodes for High Rate Microbial Electrosynthesis of Acetate from Carbon Dioxide.

Carbon-based products are crucial to our society, but their production from fossil-based carbon is unsustainable. Production pathways based on the reuse of CO2 will achieve ultimate sustainability. Furthermore, the costs of renewable electricity production are decreasing at such a high rate, that electricity is expected to be the main energy carrier from 2040 onward. Electricity-driven novel processes that convert CO2 into chemicals need to be further developed. Microbial electrosynthesis is a biocathode-driven process in which electroactive microorganisms derive electrons from solid-state electrodes to catalyze the reduction of CO2 or organics and generate valuable extracellular multicarbon reduced products. Microorganisms can be tuned to high-rate and selective product formation. Optimization and upscaling of microbial electrosynthesis to practical, real life applications is dependent upon performance improvement while maintaining low cost. Extensive biofilm development, enhanced electron transfer rate from solid-state electrodes to microorganisms and increased chemical production rate require optimized microbial consortia, efficient reactor designs, and improved cathode materials. This Account is about the development of different electrode materials purposely designed for improved microbial electrosynthesis: NanoWeb-RVC and EPD-3D. Both types of electrodes are biocompatible, highly conductive three-dimensional hierarchical porous structures. Both chemical vapor deposition (CVD) and electrophoretic deposition were used to grow homogeneous and uniform carbon nanotube layers on the honeycomb structure of reticulated vitreous carbon. The high surface area to volume ratio of these electrodes maximizes the available surface area for biofilm development, i.e., enabling an increased catalyst loading. Simultaneously, the nanostructure makes it possible for a continuous electroactive biofilm to be formed, with increased electron transfer rate and high Coulombic efficiencies. Fully autotrophic biofilms from mixed cultures developed on both types of electrodes rely on CO2 as the sole carbon source and the solid-state electrode as the unique energy supply. We present first the synthesis and characteristics of the bare electrodes. We then report the outstanding performance indicators of these novel biocathodes: current densities up to -200 A m-2 and acetate production rates up to 1330 g m-2 day-1, with electron and CO2 recoveries into acetate being very close to 100% for mature biofilms. The performance indicators are still among the highest reported by either purposely designed or commercially available biocathodes. Finally, we made use of the titration and off-gas analysis sensor (TOGA) to elucidate the electron transfer mechanism in these efficient biocathodes. Planktonic cells in the catholyte were found irrelevant for acetate production. We identified the electron transfer to be mediated by biologically induced H2. H2 is not detected in the headspace of the reactors, unless CO2 feeding is interrupted or the cathodes sterilized. Thus, the biofilm is extremely efficient in consuming the generated H2. Finally, we successfully demonstrated the use of a synthetic biogas mixture as a CO2 source. We thus proved the potential of microbial electrosynthesis for the simultaneous upgrading of biogas, while fixating CO2 via the production of acetate.

Bringing High-Rate, CO2-Based Microbial Electrosynthesis Closer to Practical Implementation through Improved Electrode Design and Operating Conditions.

The enhancement of microbial electrosynthesis (MES) of acetate from CO2 to performance levels that could potentially support practical implementations of the technology must go through the optimization of key design and operating conditions. We report that higher proton availability drastically increases the acetate production rate, with pH 5.2 found to be optimal, which will likely suppress methanogenic activity without inhibitor addition. Applied cathode potential as low as -1.1 V versus SHE still achieved 99% of electron recovery in the form of acetate at a current density of around -200 A m(-2). These current densities are leading to an exceptional acetate production rate of up to 1330 g m(-2) day(-1) at pH 6.7. Using highly open macroporous reticulated vitreous carbon electrodes with macropore sizes of about 0.6 mm in diameter was found to be optimal for achieving a good balance between total surface area available for biofilm formation and effective mass transfer between the bulk liquid and the electrode and biofilm surface. Furthermore, we also successfully demonstrated the use of a synthetic biogas mixture as carbon dioxide source, yielding similarly high MES performance as pure CO2. This would allow this process to be used effectively for both biogas quality improvement and conversion of the available CO2 to acetate.

High Acetic Acid Production Rate Obtained by Microbial Electrosynthesis from Carbon Dioxide.

High product specificity and production rate are regarded as key success parameters for large-scale applicability of a (bio)chemical reaction technology. Here, we report a significant performance enhancement in acetate formation from CO2, reaching comparable productivity levels as in industrial fermentation processes (volumetric production rate and product yield). A biocathode current density of -102 ± 1 A m(-2) and an acetic acid production rate of 685 ± 30 (g m(-2) day(-1)) have been achieved in this study. High recoveries of 94 ± 2% of the CO2 supplied as the sole carbon source and 100 ± 4% of electrons into the final product (acetic acid) were achieved after development of a mature biofilm, reaching an elevated product titer of up to 11 g L(-1). This high product specificity is remarkable for mixed microbial cultures, which would make the product downstream processing easier and the technology more attractive. This performance enhancement was enabled through the combination of a well-acclimatized and enriched microbial culture (very fast start-up after culture transfer), coupled with the use of a newly synthesized electrode material, EPD-3D. The throwing power of the electrophoretic deposition technique, a method suitable for large-scale production, was harnessed to form multiwalled carbon nanotube coatings onto reticulated vitreous carbon to generate a hierarchical porous structure.

Wired pyrroloquinoline quinone soluble glucose dehydrogenase enzyme electrodes operating at unprecedented low redox potential.

We report unprecedented high current densities for the enzymatic oxidation of glucose already at 0 V versus Ag/AgCl. The modified electrodes were made by assembling pyrroloquinoline quinone (PQQ)-soluble glucose dehydrogenase (PQQ-sGDH) from Acinetobacter calcoaceticus with osmium-based redox polymers and a cross-linker. Both redox mediators are made of a poly(4-vinylpyridine) (PVP) polymer with Os complexes tethered to the polymer backbone via long C chains, giving the Os complexes flexibility and mobility inside the redox hydrogels. Current densities larger than 1 mA cm(-2) were measured already below 0 V with a plateau value of 4.4 mA cm(-2). Similar hydrogel electrodes comprising the same redox polymers and glucose oxidase (GOx) showed less than half the current densities of the PQQ-sGDH electrodes. The current versus potential curve dependence showed a sigmoidal shape characteristic of mediated enzyme catalysis but with a current increase versus potential less sharp than expected. Surprisingly, the midwave redox potential was positively shifted with respect to the potential of the redox mediator.

Liquid-liquid extraction of boron from continental brines by 2-butyl-1-octanol diluted in kerosene.

Lithium production from brines generates significant quantities of salts, including boron, that are not effectively utilized and end up being stored in landfills. This study delves into a novel approach for directly extracting boron from native brines without performing solar evaporation as an alternative to traditional methods based on boron extraction from ores, offering a sustainable route to producing boric acid or borax. By exploring factors such as 2-butyl-1-octanol concentration, phase volume ratio, temperature, and pH, the research scrutinizes boron extraction efficiency from two native brines sourced from the salar de Hombre Muerto in Argentina, alongside a synthetic brine simulating these native compositions. Notably, the extractant demonstrates exceptional promise due to its limited solubility in the brine, measuring at just 18 mg L-1. Optimal conditions-2 mol L-1 2-butyl-1-octanol, O/A ratio of 4, 25 °C temperature, and pH of 5.5-resulted in a remarkable 98.2% and 94.2% recovery of boron from synthetic and native brines, respectively. Importantly, this extraction process showcased minimal co-extraction of lithium, calcium, magnesium, potassium, and sodium. Leveraging these findings, a proposed flowsheet outlines a highly selective method for extracting boron from brines, presenting an alternative avenue to conventional borax production from boron ores.

Removal of the X-ray contrast media diatrizoate by electrochemical reduction and oxidation.

Due to their resistance to biological wastewater treatment, iodinated X-ray contrast media (ICM) have been detected in municipal wastewater effluents at relatively high concentrations (i.e., up to 100 µg L(-1)), with hospitals serving as their main source. To provide a new approach for reducing the concentrations of ICMs in wastewater, electrochemical reduction at three-dimensional graphite felt and graphite felt doped with palladium nanoparticles was examined as a means for deiodination of the common ICM diatrizoate. The presence of palladium nanoparticles significantly enhanced the removal of diatrizoate and enabled its complete deiodination to 3,5-diacetamidobenzoic acid. When the system was employed in the treatment of hospital wastewater, diatrizoate was reduced, but the extent of electrochemical reduction decreased as a result of competing reactions with solutes in the matrix. Following electrochemical reduction of diatrizoate to 3,5-diacetamidobenzoic acid, electrochemical oxidation with boron-doped diamond (BDD) anodes was employed. 3,5-Diacetamidobenzoic acid disappeared from solution at a rate that was similar to that of diatrizoate, but it was more readily mineralized than the parent compound. When electrochemical reduction and oxidation were coupled in a three-compartment reactor operated in a continuous mode, complete deiodination of diatrizoate was achieved at an applied cathode potential of -1.7 V vs SHE, with the released iodide ions electrodialyzed in a central compartment with 80% efficiency. The resulting BDD anode potential (i.e., +3.4-3.5 V vs SHE) enabled efficient oxidation of the products of the reductive step. The presence of other anions (e.g., chloride) was likely responsible for a decrease in I(-) separation efficiency when hospital wastewater was treated. Reductive deiodination combined with oxidative degradation provides benefits over oxidative treatment methods because it does not produce stable iodinated intermediates. Nevertheless, the process must be further optimized for the conditions encountered in hospital wastewater to improve the separation efficiency of halide ions prior to the electrooxidation step.

A novel three-dimensional macrocellular carbonaceous biofuel cell.

Here we report the first membrane-free biofuel cell obtained using three-dimensional carbonaceous foam electrodes. We first developed a new synthetic pathway to produce a new carbonaceous foam electrode material bearing porosity both on the meso and macroporous scales. We proved that by increasing the porosity of our three-dimensional foams we could increase the current density of our modified electrodes. Then, by choosing the right combination of enzyme and mediator, and the right loading of active components, we achieved high current densities for an anodic system. Finally, we combined the improved cathode and anode to build a new membrane-free hybrid enzymatic biofuel cell consisting of a mediated anode and a mediator-free cathode.

Water Kefir Grains-Microbial Biomass Source for Carbonaceous Materials Used as Sulfur-Host Cathode in Li-S Batteries.

Nowadays, the use of biomass to produce cathode materials for lithium-sulfur (Li-S) batteries is an excellent alternative due to its numerous advantages. Generally, biomass-derived materials are abundant, and their production processes are environmentally friendly, inexpensive, safe, and easily scalable. Herein, a novel biomass-derived material was used as the cathode material in Li-S batteries. The synthesis of the new carbonaceous materials by simple carbonization and washing of water kefir grains, i.e., a mixed culture of micro-organisms, is reported. The carbonaceous materials were characterized morphologically, texturally and chemically by using scanning electron microscopy, N2 adsorption-desorption, thermogravimetric analysis, X-ray diffraction, and both Raman and X-ray photoelectron spectroscopy. After sulfur infiltration using the melt diffusion method, a high sulfur content of ~70% was achieved. Results demonstrated that the cell fitted with a cathode prepared following a washing step with distilled water after carbonization of the water kefir grains only, i.e., not subjected to any chemical activation, achieved good electrochemical performance at 0.1 C. The cell reached capacity values of 1019 and 500 mAh g-1 sulfur for the first cycle and after 200 cycles, respectively, at a high mass loading of 2.5 mgS cm-2. Finally, a mass loading study was carried out.

Efficient direct electron transfer of PQQ-glucose dehydrogenase on carbon cryogel electrodes at neutral pH.

We present a comprehensive study of the direct electron transfer reaction of soluble PQQ-GDH from Acinetobacter calcoaceticus. Wild-type PQQ-sGDH nonspecifically adsorbed on carbon cryogel electrodes retained its enzymatic activity for glucose and maltose oxidation at pH 7.2 and 37 °C. The cyclic voltammograms in the absence of enzymatic substrate showed 2 redox peaks that suggest a two-step, one-electron oxidation/reduction of PQQ. Calibration curves showed a linear amperometric response for a wide glucose concentration range, including the values normally found in blood. At saturation, the catalytic current reached 0.93 mA cm(-2). Altogether the experimental results suggest that the amperometric output of the electrodes and the shape of the calibration curves represent a combination of the intrinsic enzyme kinetics, the maximum rate of heterogeneous electron transfer and the substrate accessibility to the enzyme's active center caused by the confinement of the enzyme into the mesoporous structure. A new mutant enzyme, N428C, developed in our group that shows almost twice the maximum catalytic activity in homogeneous experiments in solution, also showed a DET signal on carbon cryogel electrodes for glucose electro-oxidation. The higher activity for the mutant enzyme was also verified on the electrode surface.

Performance of a double-slope solar still for the concentration of lithium rich brines with concomitant fresh water recovery.

Lithium recovery from brines has become a hot topic. The current evaporitic technology is slow, and serious environmental concern has been raised regarding the large volumes of water used, relating both to brine concentration through evaporation, and intensive pumping of fresh water needed in the fine chemical processing to produce high purity lithium carbonate. In this work, an experimental and theoretical analysis of brine desalination using a double-slope Solar Still was carried out. The Solar Still was installed right next to an existing lithium mining facility in northwest Argentina, and was tested with native high salinity lithium rich brine for a continuous year under the typical weather conditions of lithium deposits: high altitude, large thermal amplitude between day and night, strong winds, and high solar radiation. The performance of the solar still as an evaporator was compared with that of a PAN evaporimeter class A, and correlated to experimentally determined weather parameters. While the performance of the Solar Still for brine concentration was below that of open air evaporation, the Solar Still allowed for the production of an average of 2 L day-1 m-2 of distilled water, in marked contrast with current practice. Numerical simulations allowed us to quantify heat exchanges in both the Solar Still and the open air system.

From dynamic measurements of photosynthesis in a living plant to sunlight transformation into electricity.

We propose here a new method for the direct and continuous measurement of O(2) and glucose generated during photosynthesis. Our system is based on amperometric enzyme biosensors comprising immobilized redox enzymes (glucose oxidase (GOx) and bilirubin oxidase (BOD)) and redox hydrogels "wiring" the enzyme reaction centers to electrodes. We found that these electrodes, implanted into a living plant, responded in real time to visible light as an external stimulus triggering photosynthesis. They proved to be highly selective and fast enough and may be a valuable tool in understanding photosynthesis kinetics. Furthermore, we demonstrate that with our electrodes we could harvest glucose and O(2) produced during photosynthesis to produce energy, transforming sunlight into electricity in a simple, green, renewable, and sustainable way.

Designing a highly active soluble PQQ-glucose dehydrogenase for efficient glucose biosensors and biofuel cells.

We report for the first time a soluble PQQ-glucose dehydrogenase that is twice more active than the wild type for glucose oxidation and was obtained by combining site directed mutagenesis, modelling and steady-state kinetics. The observed enhancement is attributed to a better interaction between the cofactor and the enzyme leading to a better electron transfer. Electrochemical experiments also demonstrate the superiority of the new mutant for glucose oxidation and make it a promising enzyme for the development of high-performance glucose biosensors and biofuel cells.

Potential water recovery during lithium mining from high salinity brines.

Lithium extraction from continental brines involves the evaporation of large amounts of water in open air ponds, in order to concentrate the brine. The evaporitic technology implies the evaporation of large water volumes, raising environmental concerns. If we envision the use of desalination processes for the concentration of lithium-rich brines, then fresh water production/recovery becomes a process well integrated with lithium extraction. Here we apply the Pitzer thermodynamic model with effective molality to estimate activity coefficients for 8 different native brines, and for the resulting concentrated solutions produced by a hypothetical advanced desalinization technique. In all cases, rational activity coefficients deviate considerably from unity. We calculate next the least work of separation for a hypothetical desalination process for the 8 different brines. Because of the large total salinity, the calculation shows that the least work of separation ranges from 18 until 42 kJ kg-1 at nil recovery ratio, and escalating from those numbers as more water is recovered. We can also predict the boiling point elevation, the vapour pressure lowering, and the osmotic pressure. Our calculations show that results are not strictly proportional to the total dissolved solids. Results are strongly dependent with the specific chemical composition of each brine, with the amount of divalent ions (Mg-Ca-SO42-) in particular strongly influencing calculations. Fresh water and lithium minerals production could be part of a single integrated production system.

Membrane electrolysis for the removal of Mg2+ and Ca2+ from lithium rich brines.

Lithium is today an essential raw material for renewable energy technologies and electric mobility. Continental brines as present in the Lithium Triangle are the most abundant and the easiest to exploit lithium sources. Lithium is present in diluted concentrations together with different ions, and it is imperative to fully remove both magnesium and calcium before lithium carbonate can be precipitated. Here we use membrane electrolysis as a novel method to generate hydroxyl groups in situ in a two-chamber electrochemical cell with a side crystallizer, omitting the need for chemical addition and not leading to substantial loss of lithium rich brine. Batch electrolysis experiments fully removed more than 99.99% of both Mg2+ and Ca2+ for three different native South-American brines treated at current densities ranging from 27 to 350 A m-2 (final concentrations were below ICP detection limit: < 0.05 mg L-1). For a brine containing 3090 mg L-1 of Mg2+ and 685 mg L-1 of Ca2+, 62 kWh m-3 are needed for the full removal of both cations when a current density of 223 A m-2 is employed. Most importantly, the Li+ concentration in the brine is not affected. The removed cations are precipitated as Mg(OH)2 and Ca(OH)2. Our process has the potential to simultaneously recover lithium, magnesium, and calcium compounds, minimizing waste production.

Lithium recovery from brines: A vital raw material for green energies with a potential environmental impact in its mining and processing.

The electrification of our world is driving a strong increase in demand for lithium. Energy storage is paramount in electric and hybrid vehicles, in green but intermittent energy sources, and in smart grids in general. Lithium is a vital raw material for the build-up of both currently available lithium-ion batteries, and prospective next generation batteries such as lithium-air and lithium sulphur. The continued availability of lithium can only rely on a strong increase of mining and ore processing. It would be an inconsistency if the increased production of lithium for a more sustainable society would be associated with non-sustainable mining practices. Currently 2/3 of the world production of lithium is extracted from brines, a practice that evaporates on average half a million litres of brine per ton of lithium carbonate. Furthermore, the extraction is chemical intensive, extremely slow, and delivers large volumes of waste. This technology is heavily dependent on the geological structure of the deposits, brine chemical composition and both climate and weather conditions. Therefore, it is difficult to adapt from one successful exploitation to new deposits. A few years of simulations and piloting are needed before large scale production is achieved. Consequently, this technology is struggling with the current surge in demand. At time of writing, only 5 industrial scale facilities are in operation worldwide, highlighting the shortcomings in this technology. Both mining companies and academics are intensively searching for new technologies for lithium recovery from brines. However, focus on the chemistry of brine processing has left unattended the analysis of the sustainability of the overall process. Here we review both the current available technology and new proposed methodologies. We make a special focus on an overall sustainability analysis, with particular emphasis to the geological characteristics of deposits and water usage in relation to mining processes.

SR-XRD in situ monitoring of copper-IUD corrosion in simulated uterine fluid using a portable spectroelectrochemical cell.

The objective of this work is to study the initial corrosion of copper in the presence of gold when placed in simulated uterine fluid in order to better understand the evolution of active components of copper-IUDs. In order to carry out this study, a portable cell was designed to partially simulate the uterine environment and provide a way of tracking the chemical changes occurring in the samples in situ within a controlled environment over a long period of time using synchrotron spectroelectrochemistry. The dynamically forming crystalline corrosion products are determined in situ for a range of copper-gold surface ratios over the course of a 10-day experiment in the cell. It is concluded that the insoluble deposits forming over this time are not the origin of the anticonception mechanism.