Rafael Trócoli

An Aqueous Zinc‐Ion Battery Based on Copper Hexacyanoferrate

A 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. The system shows cyclability, rate capability, and specific energy values near to those of lithium-ion organic batteries based on Li4 Ti5 O12 and LiFePO4 at 10 C. The effects of Zn(2+) intercalation and H2 evolution on the performance of the battery are discussed in detail. In particular, it has been observed that hydrogen evolution can cause a shift in pH near the surface of the zinc electrode, and favor the stabilization of zinc oxide, which decreases the performance of the battery. This mechanism is hindered when the surface of zinc becomes rougher.

Selectivity of a Lithium‐Recovery Process Based on LiFePO4

The 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.

Nickel Hexacyanoferrate as Suitable Alternative to Ag for Electrochemical Lithium Recovery

Currently, Li is mainly produced through evaporation of Li-rich brines obtained from 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. Various electrochemical methods have been proposed as alternatives, but they use expensive metals such as Ag or Pt, thus rendering these methods economically unacceptable. In this work, we present KNiFe(CN)6 , an abundant and environmentally friendly material, as alternative to these expensive components. The Prussian blue derivate has a higher affinity toward cations (Na(+) or K(+) ) than for Li(+) . Additionally, the use of KNiFe(CN)6 permits the utilization of seawater or brine water as recovery solution, thus reducing the consumption of fresh water, which is typically a scarce element in Li production sites.

Ultrafast Dischargeable LiMn2O4 Thin-Film Electrodes with Pseudocapacitive Properties for Microbatteries

LiMn2O4 (LMO) thin films are deposited on Si-based substrates with Pt current collector via multi-layer pulsed-laser-deposition technique. The LMO thin films feature unique kinetics that yield outstanding electrochemical cycling performance in an aqueous environment. At extremely high current densities of up to 1880 μA cm-2 (≈ 348 C), a reversible capacity of 2.6 μAh cm-2 is reached. Furthermore, the electrochemical cycling remains very stable for over 3500 cycles with a remarkable capacity retention of 99.996% per cycle. We provide evidence of significant nondiffusion-controlled, pseudocapacitive-like storage contribution of the LMO electrode.

Lithium recovery by means of electrochemical ion pumping: a comparison between salt capturing and selective exchange.

Currently, 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. In this work a comparison between the salt capturing method, based on silver / silver chloride reaction, and the selective exchange method, based on ion intercalation reaction in a Prussian Blue derivative, is performed in terms of energy consumption. In particular, the energy consumption is divided in thermodynamic and kinetic contribution, and the theoretical calculations are compared with the experimental results. The experimental results show a good agreement with the theoretical calculation. The selective exchange method shows superior performances to the salt exchange in terms of purity and efficiency, however the energy consumption is higher.

Synthesis of nanostructured LiMn2O4 thin films by glancing angle deposition for Li-ion battery applications.

The development of electric vehicles and portable electronic devices demands lighter and thinner batteries with improved specific charge and rate capabilities. In this work, thin films of LiMn2O4 were fabricated by rf magnetron sputtering. Glancing angle deposition is introduced as a promising approach for fabrication of porous cathode thin films with 2.6 times the capacity in comparison with conventionally sputtered films of the same thickness. Surface morphology and crystallinity of the films are studied along with their electrochemical performance in an aqueous electrolyte. The glancing angle deposited films can reach a rate capability of up to 4 mA cm-2 with minimal energy loss, and a life cycle longer than 100 charge/discharge cycles.

High Specific Power Dual-Metal-Ion Rechargeable Microbatteries Based on LiMn2O4 and Zinc for Miniaturized Applications

Miniaturized rechargeable batteries with high specific power are required for substitution of the large sized primary batteries currently prevalent in integrated systems since important implications in dimensions and power are expected in future miniaturized applications. Commercially available secondary microbatteries are based on lithium metal which suffers from several well-known safety and manufacturing issues and low specific power when compared to (super) capacitors. A high specific power and novel dual-metal-ion microbattery based on LiMn2O4, zinc, and an aqueous electrolyte is presented in this work. Specific power densities similar to the ones exhibited by typical electrochemical supercapacitors (3400 W kg-1) while maintaining specific energies in the range of typical Li-ion batteries are measured (∼100 Wh kg-1). Excellent stability with very limited degradation (99.94% capacity retention per cycle) after 300 cycles is also presented. All of these features, together with the intrinsically safe nature of the technology, allow anticipation of this alternative micro power source to have high impact, particularly in the high demand field of newly miniaturized applications.

Effect of Pt and Au current collector in LiMn2O4 thin film for micro-batteries

The crystal orientation and morphology of sputtered LiMn2O4 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 LiMn2O4 a change in the preferential orientation of the grains from (111) to (400). In addition, LiMn2O4 thin films deposited on Au show a higher porosity than films deposited on Pt. These structural differences cause an improvement in the electrochemical performances of the thin films deposited on Au, with up to 50% more specific charge. Aqueous cells using thin film based on LiMn2O4 sputtered on Au or Pt as the cathode electrode present a similar retention of specific charge, delivering 85% and 100%, respectively, of the initial values after 100 cycles. The critical role of the nature of the substrate used in the morphology and electrochemical behaviour observed could permit the exploration of similar effects for other lithium intercalation electrodes.