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. 2020 Apr 20;5(17):10115-10122.
doi: 10.1021/acsomega.0c00728. eCollection 2020 May 5.

ϵ-FeOOH: A Novel Negative Electrode Material for Li- and Na-Ion Batteries

Kazuhiko Mukai  1 , Ikuya Yamada  2
Affiliations

ϵ-FeOOH: A Novel Negative Electrode Material for Li- and Na-Ion Batteries

Kazuhiko Mukai et al. ACS Omega. .

Abstract

The demand for eco-friendly materials for secondary batteries has stimulated the exploration of a wide variety of Fe oxides, but their potential as electrode materials remains unknown. In this contribution, ϵ-FeOOH was synthesized using a high-pressure/high-temperature method and examined for the first time in nonaqueous Li and Na cells. Under a pressure of 8 GPa, α-FeOOH transformed into ϵ-FeOOH at 400 °C and then decomposed into α-Fe2O3 and H2O above 500 °C. Here, FeO6 octahedra form [2 × 1] tunnels in α-FeOOH or [1 × 1] tunnels in ϵ-FeOOH. The ϵ-FeOOH/Li cell exhibited a rechargeable capacity (Q recha) of ∼700 mA h·g-1 at 0.02-3.0 V, whereas the ϵ-FeOOH/Na cell indicated a Q recha of less than 30 mA h·g-1 at 0.02-2.7 V. The discharge and charge profiles of ϵ-FeOOH and α-FeOOH were similar, but the rate capability of ϵ-FeOOH was superior to that of α-FeOOH.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Crystal structures of (a) α-FeOOH (goethite), (b) β-FeOOH (akaganeite), (c) γ-FeOOH (lepidocrocite), (d) δ-FeOOH (feroxyhyte), and (e) ϵ-FeOOH.
Figure 2
Figure 2
XRD patterns of (a) α-FeOOH (pristine) and (b)–(i) HP-/HT-treated samples in order of increasing treatment temperature from top to bottom. Red and blue stars indicate diffraction lines from ϵ-FeOOH and Fe2O3, respectively.
Figure 3
Figure 3
SEM images of (a) α-FeOOH (pristine), (b) HP(100 °C), (c) HP(200 °C), (d) HP(400 °C), (e) HP(500 °C), and (f) HP(800 °C). According to XRD measurements, the major phase is α-FeOOH for HP(100 °C) and HP(200 °C), ϵ-FeOOH for HP(400 °C) and HP(500 °C), and Fe2O3 for HP(800 °C). FE-SEM images of α-FeOOH (pristine) at the (g) 1 μm scale and (h) 500 nm scale and (i) HP(500 °C) at the 1 μm scale.
Figure 4
Figure 4
Discharge and charge curves of Li cells with (a) α-FeOOH (pristine) and (b–h) HP-/HT-treated samples in order of increasing treatment temperature from top to bottom. The cells were operated at a current of 0.1 mA. The red lines in (a–h) are the discharge and charges curves at the first cycle. dQdis/dV (or dQcha/dV) curves of the (i) α-FeOOH (pristine), (j) HP(400 °C), and (k) HP(800 °C) samples. The red and black lines in (i–k) are the dQdis/dV (or dQcha/dV) curves at the first and second cycles, respectively.
Figure 5
Figure 5
Extended cycle tests on the (a) HP(300 °C) and (b) HP(400 °C) samples at a current of 0.3 mA. For clarity, the discharge curve for the first cycle is not displayed. (c) Qcha as a function of cycle number. The blue lines in (b) are the discharge and charge curves after the 30th cycle operated at a current of 0.1 mA.
Figure 6
Figure 6
(a) Discharge and charge curves of the Na cell with the HP(400 °C) sample operated at a current of 0.1 mA and 25 °C. (b) Corresponding dQdis/dV (or dQcha/dV) curve at the first cycle.
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