Lithium battery materials can be advantageously used for the selective sequestration of lithium ions from natural resources, which contain other cations in high excess. However, for practical ...applications, this new approach for lithium production requires the battery host materials to be stable over many cycles while retaining the high lithium selectivity. Here, a nearly symmetrical cell design was employed to show that LiFePO4 shows good capacity retention with cycling in artificial lithium brines representative of brines from Chile, Bolivia and Argentina. A quantitative correlation was identified between brine viscosity and capacity degradation, and for the first time it was demonstrated that the dilution of viscous brines with water significantly enhanced capacity retention and rate capability. The electrochemical and X‐ray diffraction characterisation of the cycled electrodes also showed that the high lithium selectivity was preserved with cycling. Raman spectra of the cycled electrodes showed no signs of degradation of the carbon coating of LiFePO4, while scanning electron microscopy images showed signs of particle cracking, thus pointing towards interfacial reactions as the cause of capacity degradation.
Brine is fine: The electrochemical sequestration of lithium from brines representative of the largest lithium resources in South America is explored, using a battery host material (LiFePO4) as a sustainable approach of lithium production. The brine viscosity is found to critically affect the cycling stability and rate capability, and, surprisingly, significant improvements are achieved by simple brine dilution. Post‐mortem characterisation suggests that interfacial side‐reactions and particle cracking limit the long‐term stability.
Lithium battery materials can be advantageously used for the selective sequestration of lithium ions from natural resources, which contain other cations in high excess. However, for practical ...applications, this new approach for lithium production requires the battery host materials to be stable over many cycles while retaining the high lithium selectivity. Here, a nearly symmetrical cell design was employed to show that LiFePO
shows good capacity retention with cycling in artificial lithium brines representative of brines from Chile, Bolivia and Argentina. A quantitative correlation was identified between brine viscosity and capacity degradation, and for the first time it was demonstrated that the dilution of viscous brines with water significantly enhanced capacity retention and rate capability. The electrochemical and X-ray diffraction characterisation of the cycled electrodes also showed that the high lithium selectivity was preserved with cycling. Raman spectra of the cycled electrodes showed no signs of degradation of the carbon coating of LiFePO
, while scanning electron microscopy images showed signs of particle cracking, thus pointing towards interfacial reactions as the cause of capacity degradation.
Abstract
Batteries that extend performance beyond the intrinsic limits of Li-ion batteries are among the most important developments required to continue the revolution promised by electrochemical ...devices. Of these next-generation batteries, lithium sulfur (Li–S) chemistry is among the most commercially mature, with cells offering a substantial increase in gravimetric energy density, reduced costs and improved safety prospects. However, there remain outstanding issues to advance the commercial prospects of the technology and benefit from the economies of scale felt by Li-ion cells, including improving both the rate performance and longevity of cells. To address these challenges, the Faraday Institution, the UK’s independent institute for electrochemical energy storage science and technology, launched the Lithium Sulfur Technology Accelerator (LiSTAR) programme in October 2019. This Roadmap, authored by researchers and partners of the LiSTAR programme, is intended to highlight the outstanding issues that must be addressed and provide an insight into the pathways towards solving them adopted by the LiSTAR consortium. In compiling this Roadmap we hope to aid the development of the wider Li–S research community, providing a guide for academia, industry, government and funding agencies in this important and rapidly developing research space.
The parasitic reactions associated with reduced oxygen species and the difficulty in achieving the high theoretical capacity have been major issues plaguing development of practical non-aqueous Li-O2 ...batteries. We hereby address the above issues by exploring the synergistic effect of 2,5-di-tert-butyl-1,4- benzoquinone and H2O on the oxygen chemistry in a non-aqueous Li-O2 battery. Water stabilizes the quinone monoanion and dianion, shifting the reduction potentials of the quinone and monoanion to more positive values (vs. Li+). When water and the quinone are used together in a (largely) non-aqueous Li-O2 battery, the cell discharge operates via a two-electron oxygen reduction reaction to form Li2O2, the battery discharge voltage, rate, capacity all being considerably increased and fewer side reactions being detected; Li2O2 crystals can grow up to 30 um, more than an order of magnitude larger than cases with the quinone alone or without any additives, suggesting that water is essential to promoting a solution dominated process with the quinone on discharging. The catalytic reduction of O2 by the quinone monoanion is predominantly responsible for the attractive features mentioned above. Water stabilizes the quinone monoanion via hydrogen bond formation and by coordination of the Li+ ions, and it also helps increase the solvation, concentration, life time and diffusion length of reduced oxygen species that dictate the discharge voltage, rate and capacity of the battery. When a redox mediator is also used to aid the charging process, a high-power, high energy- density, rechargeable Li-O2 battery is obtained.