One-dimensional (1D) olivine iron phosphate (FePO4) is widely proposed for electrochemical lithium (Li) extraction from dilute water sources, however, significant variations in Li selectivity were observed for particles with different physical attributes. Understanding how particle features influence Li and sodium (Na) co-intercalation is crucial for system design and enhancing Li selectivity. Here, we investigate a series of FePO4particles with various features and revealed the importance of harnessing kinetic and chemo-mechanical barrier difference between lithiation and sodiation to promote selectivity. The thermodynamic preference of FePO4provides baseline of selectivity while the particle features are critical to induce different kinetic pathways and barriers, resulting in different Li to Na selectivity from 6.2 × 102to 2.3 × 104. Importantly, we categorize the FePO4particles into two groups based on their distinctly paired phase evolutions upon lithiation and sodiation, and generate quantitative correlation maps among Li preference, morphological features, and electrochemical properties. By selecting FePO4particles with specific features, we demonstrate fast (636 mA/g) Li extraction from a high Li source (1: 100 Li to Na) with (96.6 ± 0.2)% purity, and high selectivity (2.3 × 104) from a low Li source (1: 1000 Li to Na) with (95.8 ± 0.3)% purity in a single step.
The drawbacks of common anodes in lithium-ion batteries (LIBs) and hybrid supercapacitors (HSCs), such as the high voltage plateau of Li4Ti5O12(1.55 V vs. Li/Li+) and the moderate capacity of graphite (372 mAh-g-1), have established a need for better materials. Conversion materials, and in particular iron oxide and CaFe2O4(CFO), have amassed recent attention as potential anode replacements. In this study, we evaluate the material and electrochemical effects of the solution combustion synthesis (SCS) of porous CFO across novel fuel-to-oxidizer ratios and calcination temperatures. We demonstrate that nearly doubling the amount of fuel used during synthesis increases capacities between 120 and 150% at high current densities (~ 1000 mA-g-1) and across 500 additional charging-discharging cycles, an effect brought on in part by enhanced compositional purity in these samples. However, in order to ensure long-term cyclic stability, it is necessary to also calcine porous CFO to 900 °C to enhance crystallite size, particle size and spacing, and compositional purity.
more » « less- PAR ID:
- 10363329
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Scientific Reports
- Volume:
- 12
- Issue:
- 1
- ISSN:
- 2045-2322
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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