DOI: 10.1002/celc.

201800548 Articles
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Simple Microwave-Assisted Synthesis of Delafossite
5 CuFeO2 as an Anode Material for Sodium-Ion Batteries
6
7 Duck Hyun Youn+,[a, c] Yo Han Choi+,[b] Jun-Hyuk Kim,[a] Sungmin Han,[a] Adam Heller,[a] and C.
8 Buddie Mullins*[a]
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10
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A simple synthesis of microcrystalline delafossite CuFeO2 is 0.01 V and charged at 1.5 V vs Na + /Na and retained a reversible
12
reported. Rhombohedral CuFeO2 0.7–2.5 mm crystals were capacity of 240 mAh g1 at a specific current of 0.1 Ag1 after
13
obtained by heating an aqueous solution of Fe(NO3)3, Cu(NO3)2, 200 cycles. The delafossite CuFeO2 microcrystals could be a
14
and propionaldehyde to 180 8C for 2 h in a microwave oven, potential anode material for sodium-ion batteries considering
15
which enables the synthesis of the CuFeO2 microcrystals with the simple synthetic method and acceptable reversible capacity
16
significantly reduced heating time at a mild temperature. The compared to other nanostructured anode materials.
17
electrode made with the delafossite CuFeO2 discharged at
18
19
20
21 1. Introduction high reversible capacities.[16–20] Also, ternary metal oxides
22 including NiCo2O4, CoFe2O4, and MnFeO4 have been inves-
23 Because of the abundance and lesser cost of sodium, sodium- tigated to improve cycling stability due to their low cost and
24 ion batteries (NIBs) are considered as alternatives to lithium-ion potential improvement in electrical and mechanical stabilities
25 batteries (LIBs) in large-scale applications.[1–2] Finding a host for compared to those of single component metal oxides.[21–24]
26 the 1.06 Å radius Na + cation which diffuses less rapidly less As a member of the family of ternary TMOs, CuFeO2
27 than the 0.76 Å radius Li + cation, is, however, a challenge, exhibiting the so-called delafossite structure has received much
28 because the slow diffusion limits the cycling rates of the attention due to its unique crystal structure and has been
29 storage batteries.[2–3] On the cathode side, layered transition studied as a photocatalyst,[25] a catalyst,[26] and an antimicrobial
30 metal oxides and poly-anions already provide adequate specific material.[27] CuFeO2 has also recently been considered as an LIB
31 capacity and cycling stability,[4–6] but progress in NIB anode anode material,[28–30] however, it has rarely been used in NIBs.[31]
32 materials has been slower. The typical graphite anode material CuFeO2 is usually prepared by high temperature solid state
33 employed in LIBs cannot be employed in the NIB anode due to reaction (> 850 8C, > 12 h),[28] sol-gel method with an after-
34 its negligible amount of Na + ion storage,[7–8] thus opportunity treatment at high temperature (> 650 8C, 10 h),[29] or hydro-
35 exists for the development of an anode material for NIBs. thermal synthesis (180 8C, < 24 h),[27,30,32] all of which involve
36 The investigated carbon-based NIB anodes[9–10] are less high temperature and long reaction time. Thus, here we report
37 stable than their LIB counterparts, reacting with the non- progress in the development of a facile fabrication method for
38 aqueous electrolytes.[11] The massive expansion/shrinkage upon CuFeO2 and investigates its electrochemical properties as a NIB
39 sodiation/de-sodiation of the investigated elemental metal[12–13] anode.
40 and alloy NIB anodes[14–15] results in fast capacity fading.[16] One Here, we report a facile fabrication method for delafossite
41 of the promising anode materials for NIBs is transition metal CuFeO2 microcrystals by microwave heating of an aqueous
42 oxides (TMOs) such as Na2Ti3O7, Fe2O3, and SnO2 due to their precursor mixture at low temperature (180 8C) and with
43 significantly reduced reaction time (2 h). The resultant CuFeO2
44 [a] Dr. D. H. Youn,+ Dr. J.-H. Kim, S. Han, Prof. A. Heller, Prof. C. B. Mullins microcrystals exhibit rhombohedral structure with a size range
45 Department of Chemical Engineering and Department of Chemistry Center of 0.7 ~ 2.5 mm and the anodes made with CuFeO2 showed a
for Electrochemistry and Texas Materials Institute
46 University of Texas at Austin high reversible capacity of 240 mAh g1 at 100 mA g1 after 200
47 1 University Station, C0400 cycles, suggesting that they merit consideration for use in
48 Austin, TX 78712-0231, United States anodes of sodium storage batteries.
E-mail: mullins@che.utexas.edu
49 [b] Dr. Y. H. Choi+
50 Division of Advanced Nuclear Engineering
51 Pohang University of Science and Technology (POSTECH) 2. Results and Discussion
Pohang, 790-784, South Korea
52 [c] Dr. D. H. Youn+
53 Department of Chemical Engineering 2.1. Physicochemical Properties of CuFeO2
54 Kangwon National University
Chuncheon, Gangwon-do 24341, South Korea
55 [+] These authors contributed equally to this work.
Figure 1 shows the scheme employed for the synthesis of the
56 Supporting information for this article is available on the WWW under CuFeO2 microcrystals. Iron and copper precursors were dis-
57 https://doi.org/10.1002/celc.201800548 solved in water and propionaldehyde was added as a weak

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Articles
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8 Figure 1. Microwave-assisted synthesis route for the preparation of CuFeO2
9 microcrystals.

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12 reducing agent to reduce Cu2 + to Cu1 +.[27,30] Upon microwave
13 heating at 180 8C for 2 h, the delafossite CuFeO2 microcrystals
14 were easily obtained. Compared to conventional heating
15 method, microwave heating is able to heat the target material
16 by dipolar polarization and ionic conduction without heating
17 the entire furnace, which results in shorter reaction time and
18 higher reaction rate.[31,32] In this work, by using microwave
19 heating, it was possible to reduce the heating time significantly
20 under mild temperature conditions compared to the previous
21 fabrication methods which involved higher temperatures and
22 heating times.[25–30,33,34]
23 Figure 2a shows that the XRD patterns of the resulting
24 CuFeO2 microcrystals matches those of the rhombohedral
25 Figure 3. a,b) SEM images and c,d) TEM images of CuFeO2. TEM-EDS
26 mapping images of e) Cu, f) Fe, and g) O. The scale bars are of 250 nm.
27
28
29 resolution TEM image (Figure 3d) shows lattice spacings of
30 0.568 nm and 0.249 nm, corresponding to the (003) and (012)
31 planes, respectively. The TEM-EDS mapping image of Cu (Fig-
32 ure 3e) was consistent with the mapping images of Fe (Fig-
33 ure 3f) and O (Figure 3g), all showing uniform distributions of
34 the three elements.In the X-ray photoelectron spectra (XPS), the
35 Cu 2p spectra (Figure 4a) showed intense 932.0 eV and 951.8 eV
Figure 2. a) Rietveld refinement of the XRD pattern of the product CuFeO2
36
(Rwp = 4.763 %, GOF = 1.063). Black and red lines denote observed and
37 simulated XRD patterns respectively. Blue line represents the difference
38 between black and red lines. b) Structure of the delafossite CuFeO2.
39
40
41 CuFeO2 reference patterns (JCPSD 01-075-2146). Black and red
42 lines denote observed and simulated XRD patterns respectively.
43 The blue line represents the difference between the black and
44 red lines. Rietveld refinement analysis confirms that the CuFeO2
45 crystallized in a rhombohedral structure with space group R-3m
46 and the cell parameters are a = 3.036 Å and c = 17.1544 Å.
47 Based on Rietveld refinement results, the crystalline structure of
48 CuFeO2 is represented in Figure 2b. Delafossite CuFeO2 is
49 composed of alternating layers of edge-shared FeO6 octahedral
50 units and Cu ions with linear OCuO bonds, which is
51 consistent with the reported delafossite crystal structure.[27,35]
52 Figure 3a-b show scanning electron microscope (SEM)
53 images of the 0.7–2.5 mm CuFeO2 microcrystals, which are Figure 4. XPS spectra of CuFeO2 for a) Cu 2p and b) Fe 2p. XANES spectra of
CuFeO2 for c) Cu K-edge and d) Fe K-edge.
54 rhombohedral and have well-defined edges, corners and
55 surfaces. One of the microcrystals was imaged by transmission
56 electron microscopy (TEM). Similar to the SEM images, the
57 rhombohedral structure was clearly seen (Figure 3c). The high-

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1 peaks assigned to Cu + 2p3/2 and Cu + 2p1/2 and less intense
2 peaks at 934.0 eV and 953.9 eV attributed to Cu2 + 2p3/2 and
3 Cu2 + 2p1/2. The satellite peaks that were observed suggest near-
4 surface Cu2 + species.[25] In the Fe 2p spectra shown in Figure 4b,
5 the dominant 724.0 and 711.7 eV peaks are assigned to 2p1/2
6 and 2p3/2, respectively.[36] The Fe3 + peak is more intense than
7 the Fe2 + peak in the Fe 2p3/2 spectra and the presence of a
8 characteristic satellite peak for Fe3 + at 718.2 eV all indicate that
9 Fe3 + is the dominant iron species.
10 Further investigation of the oxidation states of Cu and Fe
11 by XANES (X-ray absorption near edge structure) as shown in
12 Figure 4c shows that the Cu K-edge XANES spectra of the
13 prepared CuFeO2 and of the reference Cu2O have an almost
14 identical edge rising peak shape and position, indicating similar
15 oxidation states. The characteristic pre-edge peak of Cu1 + at
16 around 8982 eV, due to the dipole transition for the Cu + state,
17 appear in both the CuFeO2 and the Cu2O, further confirming
18 that the oxidation state of Cu in CuFeO2 is Cu1 +.[25] The Fe K-
19 edge XANES spectra of the prepared CuFeO2 showed an edge-
20 rising position (7122 eV) and shape that were similar to the
21 reference Fe2O3, i. e. that oxidation state of Fe in the CuFeO2 is
22 Fe3 +.[26]
23 The textural properties of the CuFeO2 microcrystals were
24 characterized by their N2-sorption isotherm. The surface area
25 and pore size distribution (PSD) were determined by the
26 Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH)
27 methods, respectively. The BET surface area of the CuFeO2
28 derived from a type IV isotherm, was approximately 20 m2/g
29 (Figure S1a) and the average pore size was 5.3 nm (Figure S1b),
30 indicative of mesopores.
31
32
33 2.2. Electrochemical Properties of CuFeO2 Electrodes
34
35 The CuFeO2 electrodes were galvanostatically cycled in the
36 voltage range of 0.01–1.5 V at a current density of 0.1 Ag1. The
37 1st, 10th, 50th, 100th, and 200th cycle voltage profiles are
38 shown in Figure 5a. The first cycle discharge and charge
39 capacities were 408 and 248 mAh g1 implying an initial
40 Coulombic efficiency of 60.7 % (Figure 5b). The initial capacity
41 loss is attributed to decomposition of electrolyte and formation
42 of the solid electrolyte interphase (SEI). The initial capacity loss
43 of the CuFeO2 electrode is smaller than that of other nano-
44 crystalline and NIB anodes, where Coulombic efficiencies lower
45 than 50 % are frequently observed.[12,15,19] During the first
46 discharge half cycle, plateaus at 0.75 V and 0.35 V result
47 respectively from reduction of CuFeO2 to Cu, Fe, and Na2O
48 (CuFeO2 + 4Na + + 4e!Cu + Fe + 2Na2O) and SEI formation.
49 After the first discharge half cycle, the plateaus observed near
50 0.45 V are also due to the reduction of Cu2O and Fe2O3 to Cu
51 and Fe.[16,37] The voltage profiles were not significantly changed
52 after the 10th cycle with a reversible capacity of 270 mAh g1 at
53 the 100th cycle suggesting promising cycling stability for the
54 CuFeO2 electrode. Figure S2 shows a cyclic voltammogram (CV)
55 for the CuFeO2 electrode at a scan rate of 0.1 mV s1. The CV
56 also shows a cathodic peak near 0.45 V attributed to reduction
57 of Cu2O and Fe2O3 to Cu and Fe metals, respectively. During the
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Articles
Figure 5. a) Voltage profiles of the CuFeO2 sodium anode. b) Dependences
of the specific capacity and the Coulombic efficiency on the cycle number at
a constant specific current of 0.1 Ag1. c) Dependence of the specific
capacity on the specific current. d) Nyquist plot of the CuFeO2 electrode.
anodic scan, a broad peak at around 1.0 ~ 1.3 V is observed,
indicative of the oxidation of Cu and Fe (2Fe + 3Na2O!Fe2O3 +
6Na + + 6e and 2Cu + Na2O!Cu2O + 2Na + + 2e).[16,37]
Figure S3 shows the XRD patterns of the CuFeO2 electrode
after discharge and charge half-cycles. The characteristic peaks
of the pristine electrode disappear after the first discharge half-
cycle, implying decomposition of the CuFeO2 to Cu, Fe, and
Na2O (Figure S3a). After the first charge half-cycle where the
voltage reaches 1.5 V vs. Na + /Na, small peaks are observed at
35.88 and 36.68 corresponding to the (110) plane of Fe2O3 and
the (111) plane of Cu2O, respectively (Figure S3b). These results
indicate that the produced Fe and Cu oxidized to Fe2O3 and
Cu2O during the charge step, which is consistent with the CV
results. From the second discharge/charge steps, no clear peaks
were observed indicating the formation of amorphous species.
Figure 5b shows the cycle number dependence of the
specific capacity of the CuFeO2 electrode. The circles and empty
circles (which mainly lie on top of one another) denote the
discharge capacity and charge capacity, respectively. The
electrode retains a specific capacity of 255 mAh g1 at the 150th
cycle and 240 mAh g1 at the 200th cycle. Between the 10th to
200th cycle, the specific capacity of the CuFeO2 electrode
decreases by 0.26 mAh g1 per cycle. Even without the aid of
carbon support materials to produce composite materials such
as CuFeO2/CNT or CuFeO2/graphene, the CuFeO2 electrode
showed stable cycling performance and reversibility.
Figure S4 shows the SEM images of the fresh and cycled
CuFeO2 electrodes. In the fresh electrodes (Figure S4a–b),
rhombohedral CuFeO2 microcrystals are observed with spherical
Super P carbon. Upon cycling, the surface becomes covered
with SEI (Figure S4c–d), the rhombohedral CuFeO2 crystals
disappear, and particles filled with Cu and Fe species aggregate
with the Super P carbon.
The specific current dependence of the specific capacity is
shown in Figure 5c (and the corresponding voltage profiles at
various current densities are presented in Figure S5). The
CuFeO2 electrode retains a specific capacity of 138 mAh g1 at

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1 0.5 Ag1 and 63 mAh g1 at 1.0 Ag1. When the specific current energy of metallic Cu or Fe. The obtained spectra were analyzed
2 is returned from 2.0 Ag1 to the initial 0.1 Ag1 after the 50th with ATHENA in the IFEFFIT program suite.
3 cycle, 98 % of the initial capacity is recovered, indicating good
4 reversibility for the CuFeO2 electrode. Electrochemical Measurements
5 Following the 60-cycle rate capability test, electrochemical
6 impedance spectroscopy (EIS) provided the Nyquist plot shown The CuFeO2 was dispersed in deionized water with 90 kDa CMC
(carboxymethyl cellulose) binder (Aldrich) and Super PLi carbon
7 in Figure 5d for the displayed equivalent circuit. The semicircle (Timcal) at an 8 : 1 : 1 weight ratio. The slurries were cast on to a
8 in the high frequency region is associated with the charge copper foil using a notch bar and dried at 80 8C for 12 h in a
9 transfer resistance (Rct) and the corresponding capacitance, vacuum oven. The mass loadings of all electrodes were 0.8–
10 describing the charge transfer process at the interface between 1.0 mg cm2. Coin cells were assembled with a sodium foil counter
11 the electrode and electrolyte. The measured Rct of 590.8 W is and reference electrode, a polypropylene membrane (Celgard
2400) separator, and 1.0 M NaPF6 in ethylene carbonate/ diethylene
12 larger than the similarly measured 120.0 W Rct for a CuFeO2
carbonate (1 : 1 v/v) electrolyte with the addition of 5 % fluoro-
13 electrode in a LIB under similar conditions (data not shown). ethylene carbonate (FEC) (all in an argon atmosphere glovebox).
14 Although, the CuFeO2 electrode showed promising electro- The galvanostatic charge/ discharge tests were conducted in a
15 chemical performance as a NIB anode, it will need further potential range from 0.01–1.5 V using a battery tester (Arbin, BT
16 improvements to compete with LIBs. 2143). Electrochemical impedance spectra (EIS) were recorded by a
17 potentiostat (CHI 608D, CH Instruments) with a modulation
amplitude of 5 mV in the frequency range from 105 to 101 Hz. The
18
EIS spectra were fit to an equivalent circuit by Z-view software.
19 3. Conclusions
20
21 Rhombohedral delafossite CuFeO2 crystals of 0.7–2.5 mm size
22 were made by a facile microwave heating method at the low Acknowledgements
23 temperature of 180 8C in 2 hours. The anode made with the
24 microcrystalline CuFeO2 electrode retained a high reversible This work was generously supported by the Welch Foundation
25 capacity of 240 mAh g1 at 100 mA g1 rate after 200 cycles and through grants F-1131 (A.H.) and F-1436 (C.B.M) as well as the
26 a good rate capability (98 % of capacity retention) suggesting National Science Foundation grant number CBET-1603491
27 that the delafossite CuFeO2 could be a useful anode material in (C.B.M.). This study was also supported by 2017 Research Grant
28 NIBs. from Kangwon National University (D1001205-01-01) and the
29 National Research Foundation of Korea (NRF) grant funded by the
30 Korea government (MSIP; Ministry of Science, ICT & Future
31 Experimental Section Planning) (No. 2018R1C1B5044828).
32
33 Synthesis of Delafossite CuFeO2
34
Under vigorous stirring, 2.02 g of Fe(NO3)3 · 9H2O and 1.2 g of
Conflict of Interest
35 Cu(NO3)2 · 3H2O were dissolved in 40 ml of water; 0.1 mol (4 g) of
36 NaOH was added, followed by 0.5 ml of propionaldeyde. The The authors declare no conflict of interest.
37 mixture was transferred to a Teflon reactor and heated by a
38 microwave oven (300 W) for 2 h. After filtering and washing with a
copious water-volume, the resultant powder was oven-dried at Keywords: copper iron oxide · delafossite · electrochemistry ·
39 materials science · sodium-ion batteries
80 8C for 12 h.
40
41
42 Material Characterization
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