Preparation of a NaFePO4 Cathode Material via Electrochemical Sodiation of FePO4 Layers on Al Substrates
Corresponding email: fitria@mipa.uns.ac.id
Published at : 20 Jan 2022
Volume : IJtech
Vol 13, No 1 (2022)
DOI : https://doi.org/10.14716/ijtech.v13i1.4306
Rahmawati, F., Romadhona, D.A.N., Paramita, D.D.Lestari, W.W., 2022. Preparation of a NaFePO4 Cathode Material via Electrochemical Sodiation of FePO4 Layers on Al Substrates. International Journal of Technology. Volume 13(1), pp. 168-178
| Fitria Rahmawati | Research Group of Solid-State Chemistry & Catalysis, Chemistry Department, Universitas Sebelas Maret, Jl. Ir. Sutami 36 A Kentingan, Surakarta, 57126, Indonesia |
| Dwi Aman Nur Romadhona | Research Group of Solid-State Chemistry & Catalysis, Chemistry Department, Universitas Sebelas Maret, Jl. Ir. Sutami 36 A Kentingan, Surakarta, 57126, Indonesia |
| Desi Dyah Paramita | Research Group of Solid-State Chemistry & Catalysis, Chemistry Department, Universitas Sebelas Maret, Jl. Ir. Sutami 36 A Kentingan, Surakarta, 57126, Indonesia |
| Witri Wahyu Lestari | Research Group of Inorganic Materials, Chemistry Department, Universitas Sebelas Maret, Jl. Ir. Sutami 36 A Kentingan, Surakarta, 57126, Indonesia |
In
this research, a cyclic voltammetry (CV) method was applied to intercalate Na+
into an FePO4/Al substrate to produce NaFePO4/Al as a
potential cathode material. The sodiation was conducted directly to FePO4
instead of applying delithiation to LiFePO4 followed by sodiation,
as was done in previous research. CV was conducted within a potential window of
2.0–4.0 V using a scan rate of 0.05 mVs-1. The result was compared
to LiFePO4/Al treated with a similar method. The various scan rate
was then applied to understand its effect on the electrochemical activity
recorded in the voltammogram and its impedance profile. The results show that
the CV product of FePO4/Al (NFP(A)) was crystallized in an
orthorhombic olivine NaFePO4, as a result of Le Bail refinement.
Orthorhombic Na0.7FePO4, trigonal FePO4, and monoclinic
FePO4 were presented as secondary phases. Meanwhile, the CV product of LiFePO4/Al
(NFP(B)) was also crystallized in olivine NaFePO4 and possessed
secondary phases similar to NFP(A) with an additional Fe2O3
phase. NFP(A) showed two significant peaks at 2.442 V and 3.534 V, confirming
sodiation/de-sodiation and Fe3+/Fe2+ activity,
respectively. Meanwhile, NFP(B) showed two peaks at 3.183 V and 3.04 V, corresponding
to de-lithiation and sodiation, respectively. The Nyquist plots of both
materials show a similar profile, with the impedance value of NFP(A) being
lower than that of NFP(B). This confirms that the CV treatment of FePO4/Al
is more facile than the treatment of the LiFePO4 layer, while also
producing a cathode with higher electrical conductivity. Scan rate reduction to
0.04 mVs-1 produced a much lower impedance value, confirming higher
electrical conductivity.
Electrochemical Na insertion; Electrical properties; Sodium ion-battery; Sodium iron phosphate
As important
components in Lithium Ion-Batteries (LIBs), positive electrodes or cathodes have
been studied for a few decades, with LiFePO4 (LFP) attracting the
most attention due to its favorable kinetics in the lithium
intercalation/de-intercalation process (Li et al., 2015; Sofyan et al., 2016; Yang et al., 2013), the ease of controlling its size and shape (Boesenberg et al., 2013), its low cost, its high thermal safety, its good reversible capacity, its
long cycle ability, and the fact that it is environmentally friendly (Popovi?, 2011). However, sustainable lithium supply is now a
concern because lithium is usually only
mined from limited deposits of Li2CO3 and LiOH (Kim et al., 2019).
Sodium-Ion Batteries (SIBs) might be a good alternative for LIBs due to their
high natural abundance and uniform geographic distribution on earth (Li et al., 2015; Wang et al., 2016).
Iron-based phosphates have been investigated as SIB cathodes, such as in
the molecular forms of Na2FeP2O7 (Kim et al., 2013), Na2FePO4F
(Ellis et al., 2007), Na4Fe3(PO4)2(P2O7)
(Kim et al., 2012), NaFePO4
(Kim et al., 2015),
non-crystalline iron
phosphate, FePO4 (Liu et al., 2012),
composites of amorphous FePO4 nanospheres and carbon (Fang et al., 2014), and
composites of FePO4 nanospheres and graphene (Fan et al., 2014). Even
though amorphous FePO4 is easy to synthesize, olivine NaFePO4
is preferable, especially for recently studied aqueous SIBs that require
electrode materials to have operating potentials within the electrochemical
stability window of water, in which H2 and O2 evolution
should not occur (Jeong et al., 2019). The
potential window should be between -0.83 V and 1.23 V vs. SHE at 25oC
and 1 atm (Castellan, 1983).
Meanwhile, maricite NaFePO4 is not active electrochemically within
0–4.5 V due to cavities that trap Na ions and are not connected by pathways (Prosini et al., 2014). Further
treatment to transform the maricite form into amorphous NaFePO4
provides electrochemical activity within 1.5–4.5 V (Xiong et al., 2019).
However, the potential window is above the potential window of aqueous SIB,
which is in the range of -0.5–0.85 V (vs. Ag/AgCl) in 1 M aqueous NaClO4
solution (Jeong et al., 2019).
NaFePO4 can be conventionally synthesized through solid-state
reactions using FeC2O4.2H2O, Na2CO3,
and NH4H2PO4 as precursors, followed by
calcination at 600oC for 10 h under an argon gas atmosphere (Kim et al., 2015). The
maricite structure dominates the product. However, within the maricite
structure, the diffusion channels of sodium ion transport are blocked (Heubner et al., 2017).
Meanwhile, direct chemical synthesis appears to be unsuccessful for olivine
NaFePO4 preparation. Some researchers have produced olivine
structures through ion-exchange methods using an organic-based electrochemical
insertion into delithiated-FePO4 (Oh et al., 2012; Avdeev et al., 2013; Galceran et
al., 2014). This method
requires two steps: de-lithiation and sodium insertion into the
delithiated-FePO4 in a new cell with sodium metal as the anode (Tang et al., 2016). The cyclic voltammetry profile of FePO4 with LiClO4
shows a single oxidation peak at 3.7 V and a single reduction peak at 2.85 V
indicating de-lithiation/lithiation process of LiFePO4 (Hansen et al., 2016).
Meanwhile, when the NaClO4 electrolyte was used, the peaks were at
3.65 V and 3.4 V, indicating de-lithiation of LiFePO4 and then Na+
insertion into the de-lithiated LiFePO4. The diffusion of Na+
into FePO4 is slower than that of Li+ (Heubner et al., 2016). This
means that lithiation competes the Na+ diffusion easily.
Electrochemical sodiation
was successfully applied in cyclic voltammetry mode to insert Na ions into the
FePO4 layer directly. This finding offers a simpler electrochemical
method to insert/extract Na+ directly as an alternative to the
two-step de-lithiation and sodiation method. Impedance analysis even shows a
similar semicircle trend, with a lower impedance value of NaFePO4
from FePO4, NFP(A), than the one prepared from the LiFePO4
layer, NFP(B). This research also found that by reducing the scan rate to as
low as 0.04 mVs-1, the electrical conductivity increased
for both NFP(A) and NFP (B).
This work was carried out
with the financial support of the Hibah Penelitian Dasar 2019, The Ministry of
Research, Technology, and Higher Education, the Republic of Indonesia, contract
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