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Energy & Environmental Science Cite this: Energy Environ. Sci., 2012, 5, 9487 www.rsc.org/ees Batteries for lithium recovery from brines† Mauro Pasta,‡ Alberto Battistel‡ and Fabio La Mantia* Received 25th July 2012, Accepted 17th September 2012 DOI: 10.1039/c2ee22977c Here, we report a new battery capable of efficiently recovering lithium from brines that is composed of a lithium-capturing cationic electrode (LiFePO4) and a chloride-capturing anionic electrode (Ag). It can convert a sodium-rich brine (Li : Na 1⁄4 1 : 100) into a lithium-rich solution (Li : Na 1⁄4 5 : 1) by consuming 144 W h per kg of lithium recovered. A controversial debate on the availability of lithium resources and the future needs, especially for the evermore demanding market of elec- tric vehicles, has been stimulated by the fear of a rapid and sustained increase in the price of lithium.1 As of 2012, most of the lithium (roughly 83%) is obtained from brine lakes and salt pans of limited size. In those facilities, lithium is concentrated using solar energy, a very time consuming process. Seawater contains a vast amount of lithium; however, it is dilute, so its recovery is difficult and expensive.2–4 Existing methods for purification of lithium are expensive, slow, and inefficient. Commercial operations recover lithium from salt lakes by the ‘‘lime soda evaporation process’’.5 In this process salty water is pumped into a series of shallow ponds, where it is left to evaporate for 12–18 months until the lithium chloride concentration rises up to 6000–60 000 ppm and the salts of more abundant cations tend to precipitate. Afterwards, the solution is treated with lime to remove magnesium and finally with sodium carbonate to precipitate out the insoluble lithium carbonate. This is the main process used for lithium production in South American salt lakes. Analytische Chemie – Zentrum fu€r Elektrochemie, Ruhr-Universita€t Bochum, Universita€tsstr. 150, D-44780 Bochum, Germany. E-mail: fabio. lamantia@rub.de † Electronic supplementary information (ESI) available. See DOI: 10.1039/c2ee22977c ‡ These two authors equally contributed to the manuscript. View Online / Journal Homepage / Table of Contents for this issue Dynamic Article LinksC< COMMUNICATION The amorphous Al2O3 process5 proceeds by trapping of the lithium ions with aluminum hydroxide prepared under the action of a strong base. It is suitable only for the recovery of dilute lithium in the concentration range 0.83–13.1 mg l1. In this method, a soluble aluminum salt such as AlCl3 is added to a solution that contains lithium. Next, the pH is increased until non-stoichiometric, amor- phous aluminum hydroxide precipitates. Lithium is absorbed into the precipitated aluminum hydroxide compound.2,5–8 The ion exchange techniques are based on the high selectivity of spinel manganese oxide (l-MnO2) as an absorbant for lithium ions.9,10 The absorbant material can be prepared according to two methods. In the hydrothermal method,3,10,11 a solution containing l-MnOOH and LiOH is treated in an autoclave in a temperature range of 120–170 C. The precipitate is filtered and dried, yielding a solid compound, which is then fired at a temperature of 400 C. The second method consists of preparing a finely ground mixture of lithium and manganese salts which is then calcinated. Both methods provide spinel lithium manganese oxide, which can then be treated with HCl to exchange part of the lattice Li+ with H+.9,1216 Lithium is absorbed into the delithiated manganese oxide and the circle is closed by elution with an HCl solution. Kanoh et al. were the first to propose an electrochemical method to recover lithium from aqueous solutions.17,18 They explored the possibility of recovering Li+ from seawater with a l-MnO2 modified platinum working electrode by cyclic voltammetry using a calomel and Pt-wire electrode as the reference and counter electrode, respec- tively. During Li+ insertion into MnO2, Mn(IV) is reduced to Mn(III) and when the sweep is reversed OH is oxidized to oxygen gas.17,19 At the counter electrode, oxidation to O2 and reduction of water to H2 occur during the anodic and the cathodic sweeps, respectively. In this work, a new electrochemical method for the recovery of lithium from brines is introduced; it is based on the previously developed mixing entropy battery and desalination battery.20,21 The device was designed to selectively extract lithium ions and counter Broader context Lithium is the primary component of the lithium-ion batteries destined to power the next generation of electric vehicles. The large anticipated demand for lithium has provoked debate regarding the long-term availability and price of lithium reserves. Now most lithium comes from brine lakes and salt pans but its recovery is delicate and quite expensive. In this work we developed a new battery that can efficiently recover lithium as LiCl from brines. The device is composed of a lithium-capturing cationic electrode (LiFePO4) and a chloride-capturing anionic electrode (Ag). It can convert a sodium-rich brine (Li : Na equal to 1 : 100) into a lithium-rich solution (Li : Na equal to 5 : 1) by consuming 144 W h per kg of lithium. This journal is a The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 9487–9491 | 9487 Downloaded by Stanford University on 24 October 2012 Published on 17 September 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22977CPDF Image | Batteries for lithium recovery from brines
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