Article

A Low-Cost and High-Energy Hybrid Iron-

Aluminum Liquid Battery Achieved by Deep
Eutectic Solvents
Leyuan Zhang, Changkun
Zhang, Yu Ding, Katrina
Ramirez-Meyers, Guihua Yu
ghyu@austin.utexas.edu

HIGHLIGHTS
A low-cost and high-energy Fe-Al
hybrid-flow battery

New reaction mechanism in

FeCl3$6H2O/urea/EG DES

Stable cycling achieved by

dissociating iron complexes

A low-cost and high-energy Fe-Al RFB is established for large-scale energy

storage. Using Fe catholyte at a concentration of 5 M, the Fe-Al battery can deliver
a high energy density of 166 Wh L 1. This study also furthers our fundamental
understanding about the working mechanism of Fe-urea DESs. By dissociating the
complex ions in Fe DES, the Fe-Al battery can achieve the full charge and
discharge over 1,500 hr without any capacity fading.

Zhang et al., Joule 1, 623–633

November 15, 2017 ª 2017 Elsevier Inc.
https://doi.org/10.1016/j.joule.2017.08.013
Article
A Low-Cost and High-Energy Hybrid
Iron-Aluminum Liquid Battery Achieved
by Deep Eutectic Solvents
Leyuan Zhang,1 Changkun Zhang,1 Yu Ding,1 Katrina Ramirez-Meyers,1 and Guihua Yu1,2,*

SUMMARY Context & Scale

This work demonstrates a low-cost, high-energy Fe-Al hybrid liquid battery that Given advantages of low cost,
takes advantage of the desirable properties of deep eutectic solvents (DESs). high concentration, and potential
The strategy of additive enables the full charging and discharging of the Fe-Al biodegradability, the concept of
battery with long cycle life while the stable stripping and deposition of Al is deep eutectic solvents (DESs) is
achieved. Using Fe(210) catholyte at a concentration of 5 M, the Fe-Al battery beneficial to developing cost-
can deliver a high energy density of approximately 166 Wh L 1 with an average effective and sustainable batteries
operating voltage of 1.41 V. Furthermore, by dissociating the iron complexes in with high energy density.
Fe(126) DES, the Fe-Al battery can achieve the full charge and discharge over 60 Combining environmentally
cycles without degradation. Here, an all-DES-based liquid battery is proposed friendly Al DES and Fe DES, a
with an ultrahigh concentration of redox species, resulting in high energy den- green Fe-Al hybrid liquid battery
sity. The DES maintains reduced lattice energy and depressed freezing point was designed. The stable
and provides a new platform for developing green redox species based on deposition and stripping of Al and
new chemistry. long cycling of Fe DES with high
utilization were achieved using
1,2-dichloroethane (DCE) and
INTRODUCTION
ethylene glycol (EG) as additives,
Considering the resource limitations and environmental concerns of conventional respectively. The Fe-Al hybrid
fossil fuels, energy conversion from ecologically sustainable sources, such as sun- battery delivered a high energy
light and wind, can provide green power sources in modern society. However, the density of 166.2 Wh L 1.
intermittency and unreliable stability of renewable energy systems limit their exten- Furthermore, in-depth chemical
sive application in direct power supply. Therefore, the development of efficient characterizations reveal that the
large-scale energy storage systems is necessary to make full use of the renewable excellent cycling performance of
energy resources. Fe DES should be ascribed to the
dissociation of complex ions by
Among various energy storage technologies, rechargeable batteries have been one of the EG additive. Therefore, the
the most dominant technologies for many years.1–3 In particular, redox-flow batteries strategy of additives and the
(RFBs) are considered as a promising technology for large-scale energy storage.4–7 Con- influence of coordination
ventional inorganic RFBs, such as vanadium RFBs or Zn-Br2 RFBs, have been commer- environment on electrochemical
cialized but still suffer from intrinsic disadvantages, such as the use of scarce and expen- performance provide a new
sive elements, corrosive electrolytes that raise safety concerns, and dendrite formation insight into the design of novel
(zinc).8–11 On the other hand, to improve the energy density of RFBs, lithium-based catholytes and anolytes using
hybrid-flow batteries (HFBs) with high operating voltage are being developed.12–15 DESs for redox-flow batteries.
However, limited resources, serious dendrite problems, and flammable electrolytes still
impede the extensive implementation of lithium in HFBs. As an alternative to lithium,
aluminum is attracting increasing interest due to its low cost, high abundance, and
high theoretical capacity (2,980 mAh g 1).16,17 Moreover, recent research on Al-ion bat-
teries has shown stable stripping and deposition of aluminum in Al ionic liquids (ILs) and
Al DESs without serious dendrite formation.18–20 These characteristics make aluminum a
promising potential anode in HFBs.

Joule 1, 623–633, November 15, 2017 ª 2017 Elsevier Inc. 623

In addition to broadening the operating voltage, increasing the concentration of
redox species is another strategy for enhancing the energy density of RFBs.21–23 In
traditional aqueous solutions, a solute molecule is surrounded by large amounts
of water molecules to form a solvation complex, which becomes a barrier for
achieving high concentration and, hence, high energy density in an aqueous sys-
tem.24 Recently, many metal-based DESs, such as Fe, Co, Cr, Al, Mg, and Zn,
have been easily synthesized in ambient conditions with a high concentration of
active species, which offers a potential opportunity for RFBs.25–28 Fe-based DESs,
in particular, are especially promising as cathode-active materials due to their stabil-
ity, high crust abundance, and high redox potential (Fe2+/Fe3+ at 0.77 V versus
normal hydrogen electrode).29 Meanwhile, an Al-based DES, encompassing the ad-
vantages of both Al metal and DESs, would be a better choice for anolyte compared
with Al ILs. However, due to the intrinsic properties of DESs or organic electrolytes,
the rate capability is currently not yet comparable with that of aqueous systems.

Herein, a proof-of-concept Fe-Al HFB was proposed based on Fe DES and Al DES. A
series of FeCl3$6H2O/urea/EG DESs with various molar ratios, simplified as a combina-
tion of three numbers (Fe(xxx) DESs), are obtained and the influence of EG as the addi-
tive is explored. For Al DES, 1,2-dichloroethane (DCE) is added to decrease the viscosity
and then increase the ionic conductivity. Finally, paired with Al-DES/DCE, Fe(126)
(1.8 M) and Fe(210) (5.5 M) DESs with EC/DMC (ethylene carbonate/dimethyl carbon-
ate) were selected as catholytes to test the performance of Fe-Al HFBs. This battery
has an average operating voltage of approximately 1.41 V, delivering a high energy
density of 166.2 Wh L 1 when using the Fe(210) catholyte. Moreover, we find that add-
ing EG can change the coordination environment of Fe3+ and enable the dissolution of
LiCl. The dissociation of complex cations and anions in Fe(126) catholyte from adding
EG thus improves the full charging and discharging behavior and cycling stability.
Furthermore, stable stripping and deposition of the Al anode is demonstrated by
X-ray diffraction (XRD) and scanning electron microscopy (SEM) characterization.

RESULTS AND DISCUSSION

The Proof-of-Concept Fe-Al Hybrid Liquid Battery from the Concept of Fe DES
and Al DES
As reported in the previous work, DESs can be technically and economically favor-
able for developing low-cost and high-energy flow batteries since they form a liquid
with high concentration by simply mixing the cheap raw materials at room temper-
ature. Considering the high abundance, low cost, and appropriate potentials, Fe
and Al DESs were selected as the catholyte and anolyte, respectively.

The scheme and photograph of the proof-of-concept prototype for the Fe-Al hybrid
battery system are displayed in Figure 1. An aluminum strip attached to Cu foil
serves as the anode. According to the literature,18,19 the reaction that occurs in Al
DESs is different from the one that occurs in Al ILs, due to different Al3+ coordination
environments. The Al-urea cations and Al-chloride anions in Al DES result in two
possible reactions of Al deposition and stripping as follows.

Anode reaction: 4Al2Cl7 + 3e / Al + 7AlCl4 (Equation 1)

1Materials Science and Engineering Program and
Department of Mechanical Engineering, The
University of Texas at Austin, Austin, TX 78712,
Anode reaction: 2[AlCl2$(urea)2]+ + 3e / Al + AlCl4 + 4(urea) (Equation 2) USA
2Lead Contact
As similarly discussed in our recent work,30 DCE with a low viscosity was added *Correspondence: ghyu@austin.utexas.edu
into Al DES to further decrease the viscosity and enhance the ionic conductivity of https://doi.org/10.1016/j.joule.2017.08.013

624 Joule 1, 623–633, November 15, 2017

Figure 1. The Proof-of-Concept Fe-Al Hybrid Liquid Battery
(A) Schematic of an Fe-Al battery based on DESs.
(B) The photograph of a working Fe-Al battery (top) and its schematic of device configuration
(bottom).

anolytes. Compared with the conductivity of Al DES (0.36 mS cm 1), the diluted Al
DES (denoted as Al-DES/DCE) showed a 5-fold increase in ionic conductivity to
1.9 mS cm 1. In the diluted state, the concentration of all redox species
([AlCl2(urea)n]+, Al2Cl7 , and AlCl4 ) in Al-DES/DCE was still as high as 3.2 M. In
addition, the reaction that occurred in Al-DES/DCE was similar to the Al DES reac-
tion, already reported in other literature.

For the cathode, Fe-urea DES paired with Li metal was recently demonstrated in a
high-energy green battery, but the initial coulombic efficiency and cycling perfor-
mance based on fully charging/discharging was not satisfactory. In this work, EG
was added to adjust the physical properties of FeCl3$6H2O/urea/EG DESs for the
following reasons: (1) the viscosity of EG is about 16.1 cP at 25 C, suggesting
that it may decrease the viscosity of Fe DESs; (2) the freezing point of EG is
about 10 C, giving it the potential to maintain the liquid form of Fe DESs at rela-
tively low temperatures; (3) it can dissolve LiCl salt, implying it will improve the
reversibility of redox reaction of Fe DESs. The various compositions of Fe DESs
are named by using three numbers to represent the molar ratios of FeCl3$6H2O,
urea, and EG, respectively. For example, Fe(123) DESs means the molar ratios of
FeCl3$6H2O/urea/EG is 1:2:3. Based on the knowledge of Fe-based DESs,28 three
original Fe-urea DESs are synthesized in the first step: Fe(120), Fe(110), and
Fe(210) DESs. The last number represents the molar ratio of the EG component,
meaning that EG does not exist in these three original Fe DESs.

As shown in Figure 1B, Fe DESs were injected into the quartz shell through the pre-
drilled hole in the Ti foil as catholyte. To improve the current collection efficiency,
Super P is mixed with a small amount of polyvinylidene fluoride binder coated on
the surface of Ti foil.

The Viscosity, Conductivity, and Reversibility of Various Fe DESs

As displayed in Figure 2A, various Fe DESs can be easily synthesized at ambient
environment, which also show long-term stability during storage in air (Figure S1).
With the increase of EG component in Fe DESs, the Fe3+ concentration will

Joule 1, 623–633, November 15, 2017 625

Figure 2. The Physical Properties and CVs of Various Fe DESs
(A) Photograph of various Fe DESs.
(B) Ionic conductivity of FeCl3 $6H2 O/urea/EG as a function of composition.
(C) CV curves of Fe DESs at the sweeping rate of 1 mV s 1 .
(D) Viscosity data of FeCl 3 $6H 2 O/urea/EG as a function of temperature and composition.

decrease, leading to a color change from dark to light. Fe(126) DES has a relatively
low concentration and thus forms a light-brown and transparent liquid, implying a
homogeneous and stable state. Generally, Fe DESs are more viscous than aqueous
solutions, so the ionic conductivity may be a concern in practical applications. Elec-
trochemical impedance spectroscopy (EIS) is utilized to measure the ionic conduc-
tivities of the different Fe DESs. As seen in Figure 2B, Fe(210) DES has the highest
conductivity and 120-based Fe DESs have a lower conductivity. The conductivities
of these Fe DESs (>10 mS cm 1) are much larger than that of the lithium aluminum
titanium phosphate (LATP) separator (0.1 mS cm 1), indicating that the conduc-
tivity would not limit the electrochemical performance. Cyclic voltammetry (CV)
and viscosity tests were conducted to observe the reaction reversibility of various
Fe DESs and select the appropriate catholyte for the Fe-Al battery. From the
CV curves at different sweeping rates (Figure S2) and analysis of the CV curves
at 1 mV s 1 (Figure 1C and Table S1), we find that Fe(126) DES exhibits a highly
reversible reaction compared with other samples. Differences in reversibility should
be ascribed to the different molar ratios and the influence of EG component, which
also affects viscosity. As shown in Figures 2D and S3, as the amount of EG in-
creases, the viscosity of 120-based Fe DESs initially increases and then decreases.
In contrast, the viscosity of Fe(210)-derived DESs continuously increases with the
addition of EG. Through consideration of the concentration, reversibility, and vis-
cosity of various Fe DESs, Fe(126) and Fe(210) DESs are chosen as catholytes for
the electrochemical test of the Fe-Al hybrid battery due to the high reversibility
and high concentration, respectively. To further decrease the viscosity, a
small amount of EC/DMC could be added into these two Fe DESs (denoted as
Fe-DES/EC-DMC). CV tests were conducted to assess the electrochemical stability
of EG and EC/DMC (Figure S4) and showed that no decomposition or other side
reactions occurred in the working voltage range.

626 Joule 1, 623–633, November 15, 2017

Figure 3. The Electrochemical Performance of Fe(126) DES
(A) CV curves of Fe(126) DES at different sweeping rates.
(B) Linear relationships between the oxidation and reduction peak current with the square root of
the sweeping rate.
(C) The charge and discharge capacity with corresponding coulombic efficiency of Fe(126)
catholyte when paired with Li at the current density of 0.1 mA cm 2 .
(D) Polarization curve (black) and corresponding specific power density (red) at room temperature.

The Electrochemical Performances of Fe-Li and Fe-Al Hybrid Batteries

For Fe(126) DES, CV tests were conducted at different sweeping rates using the
three-electrode system (Figure 3A). By comparing the anodic and cathodic peak cur-
rents, we find that the redox reaction of Fe(126) DES is highly reversible. Given the
high concentration of redox active material, the notable potential hysteresis, espe-
cially at high scan rates, should be attributed to the electromigration and concentra-
tion polarization. The linear relationship between the peak currents and the square
root of sweeping rate, displayed in Figure 3B, implies that the reaction in Fe(126)
DES is a diffusion-controlled process. Using the Randles-Sevcik equation below,
the diffusion coefficient was calculated to be about 2 3 10 8 cm2 s 1.

Ip = 26,900 3 n1.5AD0.5v0.5C, (Equation 3)

where Ip is peak current, n is the number of electrons involved, A is the active surface
area, D is the diffusion coefficient, v is sweeping rate, and C is the concentration of
redox species. While the derived coefficient is not comparable with those of conven-
tional redox species in water, the value is reasonable at such a high concentration,
and the diffusion process can be further facilitated by exploiting 3D current collector
in the practical battery test.

The Fe(126)-Li hybrid battery was constructed to evaluate the charging and dis-
charging behavior. Figure 3C shows the cycling performance of the Fe(126)-Li
battery, and the full charging/discharging curves are displayed in Figure S5. Under
the operating voltage of 3.45 V, a stable, long-life cycling with a high coulombic ef-
ficiency (100%–103%) is achieved. At a current density of 0.1 mA cm 2, the battery
has a volumetric capacity of about 41 Ah L 1 along with the high initial coulombic

Joule 1, 623–633, November 15, 2017 627

efficiency of 100%. Benefiting from relatively low viscosity, about 90% of the
theoretical capacity can be reversibly utilized and the average voltage difference
between charging and discharging curves is only 0.15 V. Based on the high concen-
tration of 1.7 M and high utilization, an energy density of 142.4 Wh L 1 was achieved,
which is among the highest energy densities of RFBs reported so far. The polariza-
tion curve of the Fe(126)-Li hybrid battery was obtained at room temperature
(Figure 3D). The discharging potential and current density showed a linear relation-
ship and a high power density of over 20 mW cm 2 was obtained, which is the high-
est among liquid batteries using DESs as catholytes.

To demonstrate the stable stripping/deposition of Al, ex situ XRD and scanning EM

characterizations were taken along with the CV test at different scan rates (Figure S6).
Using Al rods as the counter and reference electrodes, we obtained the CV curves
from 10 to 100 mV s 1. As seen in Figure S6A, the stripping and deposition of Al
is a highly reversible reaction in this Al-DES/DCE and the dissolution of Al occurred
at about 0 V versus Al. Figure S6B shows the XRD patterns of Al anodes before
and after electrochemical tests, which do not show any indication of impurities
(such as Al2O3 or AlCl3). Furthermore, based on the SEM images of Al anodes (Fig-
ures S6C and S6D), we believe that the dendrite problem, existing in the Li anode,
was not a serious issue in Al DESs. Above all, the stripping and deposition of Al in
Al-DES/DCE is stable and highly reversible, which makes it possible to design
advanced Al-based batteries.

The stable deposition/stripping of aluminum in the Al DES and the low-cost Fe DES
with high concentration and low viscosity enable the design of an advanced Fe-Al
HFB. Figure 4A shows the charging and discharging curves of the Fe(126)-Al hybrid
battery. Similarly, a high utilization of about 90% can be achieved, delivering a
discharge capacity of 41.4 Ah L 1. The average operating charge and discharge po-
tentials are 1.57 V and 1.41 V, respectively, resulting in a voltage gap of 0.16 V. Due
to the limitation of operating voltage, the energy density decreases to 58.1 Wh L 1,
which is lower than that of an Fe(126)-Li hybrid battery. Figure 4B shows the relation-
ship between current density and power density in the range of 0.05–1 mA cm 2.
Due to the internal resistance of the battery, the discharge potential linearly de-
creases as current density increases. Moreover, the power density turned out to
be over 1 mW cm 2 at the current density of 1 mA cm 2 associated with a discharge
voltage of roughly 1.1 V. The potential-time profile of the Fe(126)-Al hybrid battery is
presented in Figure 4C, showing that the full charging and discharging potential can
be maintained during a long operation time of 500 hr. This is consistent with the
aforementioned result of the Fe(126)-Li battery. The problem of crossover was elim-
inated by using an LATP ceramic separator, resulting in a high coulombic efficiency
of over 96% during cycling (Figure 4D). During continuous charging and discharging,
no capacity fading was found over 60 cycles with 90% utilization. Both the steady po-
tential profile and stabilized cycling performance confirmed that the redox reactions
in Fe(126)-DES/EC-DMC and Al-DES/DCE were highly reversible and stable. To
further improve the energy density of this proof-of-concept Fe-Al hybrid battery,
the Fe(210) catholyte was prepared by adding 50 mL of EC/DMC into 0.5 mL of
Fe(210) DES. The EC/DMC is meant to decrease the viscosity and is confirmed to
be electrochemically stable in the potential window. Since the concentration of
Fe(210) DES is 5.5 M, the Fe(210) catholyte still maintains a concentration of 5 M.
Paired with Li metal, the Fe(210) catholyte can also show a high utilization of about
90% in the first cycle (Figure S7A) and the power density approaches 22 mW cm 2
(Figure S7B), which is much higher than reported in previous work.29 Figure 5A
shows the initial discharging and charging profile of the Fe(210)-Al battery. Due to

628 Joule 1, 623–633, November 15, 2017

Figure 4. The Electrochemical Performance of an Fe(126)-Al Battery
(A) Charge/discharge profile of Fe(126)-DES/EC-DMC (1.7 M, 0.05 mL) paired with Al-DES/DCE
(3.2 M, 0.1 mL) at current density of 0.1 mA cm 2 .
(B) The discharge voltage and corresponding power density of an Fe(126)-Al battery at various
current densities.
(C) Representative charge and discharge profiles over time at the current density of 0.1 mA cm 2 .
(D) The charge and discharge capacity with corresponding coulombic efficiency of an Fe(126)-Al
battery at room temperature over cycling.

the increased concentration of redox species, the specific capacity soared to about
120 Ah L 1 at 0.1 mA cm 2. However, at the current density of 0.2 mA cm 2, the uti-
lization and coulombic efficiency of the initial cycling decreased (Figure S8A). The
EIS result shows that the total resistance is not very high (Figure S8B), indicating
that the performance decay at a high current density may be caused by slow
mass/ions transport. With an average voltage of approximately 1.41 V, the high en-
ergy density of 166.2 Wh L 1, based on the volume of Fe catholyte, was delivered by
this low-cost Fe(210)-Al hybrid battery. It appears that high concentration contrib-
utes to boosting the energy density, but may negatively affect the cycling perfor-
mance. Figure S8C displays the full charging and discharging of the Fe(210)-Al bat-
tery over time and suggests that the cycling performance is related to the working
mechanism of Fe(210) catholyte. To further clarify the calculation of energy density,
an example of an Fe(210)-Al battery is provided in Figure S9. The polarization curve
was measured at room temperature, as presented in Figure 5B. Similar to the
Fe(126)-Al battery, the Fe(210)-Al battery shows a limited power density of about
1.2 mW cm 2 at a current density of 1.5 mA cm 2. The potential profile with the in-
crease of current density was also measured (Figure S8D) and was consistent with the
polarization curve. To improve the power performance, we used the flow electrode
with carbon felt as current collector in the Fe side (Figure S10). As displayed in
Figures S10B and S10C, power densities of 4.5 and 5 mW cm 2 were achieved
for Fe(126)- and Fe(210)-DES/EC-DMC catholytes, respectively, both of which
were significantly higher than the static one, although still not yet comparable
with the aqueous systems. The possible reasons for the limited power density are
the low ionic conductivity of LATP membrane and the high concentration of
redox species in DESs. Therefore, modifications of the device configuration31 and

Joule 1, 623–633, November 15, 2017 629

Figure 5. The Electrochemical Performance of an Fe(210)-Al Battery
(A) The initial charge/discharge profile of Fe(210)-DES/EC-DMC (5 M, 0.03 mL) paired with Al-DES/
DCE (3.2 M, 0.18 mL) at current density of 0.1 mA cm 2 .
(B) Polarization graph showing the discharging potential and power density at room temperature.

exploitation of advanced membranes may provide a forward path to push the limit of
power density. However, considering the advantageous low cost and high energy
density, the Fe-Al battery has great potential to be applied in large-scale energy
storage.

The Working Mechanism of Fe DESs

The coordination of Fe3+ in the Fe-urea eutectic system is complicated and not well
understood, which limits the elucidation of the working mechanism of Fe-urea DESs.
Possible cathode reactions were proposed in previous reports,29,32 such as:

[FeCl2(OD)4]+ + OD + e / [Fe(OD)5]2+ + 2Cl (Equation 4)

[FeCl4] + e / [FeCl4]2 , (Equation 5)

where OD is the oxygen donor.

In this work, to understand the working mechanism the Raman spectra of various Fe
DESs were measured, as shown in Figures 6A and 6B. Interestingly, in the absence of
EG, Fe(120), Fe(110), and Fe(210) DESs had similar Raman spectra, indicating the
same coordination environment for Fe3+. The strongest peak at around 328 cm 1
corresponded to the vibration of [FeCl4] ,33–36 while the influence of EG additives
on the three original Fe DESs had a slight variation. For 120-based Fe DESs (121
and 126), adding EG immediately caused the disappearance of the [FeCl4] peak,
while the peaks corresponding to urea and EG (828, 1,020 and 1,080 cm 1)
increased (Figure S11A). For Fe(221) DES, originating from Fe(110) DES, the weak-
ened peak of [FeCl4] still existed along with the strengthened peak at
1,020 cm 1, which could be attributed to urea. For 210-based Fe DESs, a small
amount of EG did not affect the coordination of Fe3+ (Fe(421)). When the molar ratio
became 2:1:2, the peak of [FeCl4] eventually decreased considerably. However, the
feature peaks related to urea and EG did not increase strongly, as seen in Figure 6B.

To understand the redox reaction of Fe DESs, we conducted a Raman test of Fe(126)

and Fe(210) catholytes after discharging and charging. As expected, the Raman
spectra of Fe(126) catholyte had negligible changes during charging and discharg-
ing, as shown in Figure 6C, implying that the coordination of Fe3+ or Fe2+ did not
change. Since a large amount of EG caused the dissociation of [FeCl4] , we thought
Fe3+ might not have the chloride-related coordination in Fe(126) DES, merely

630 Joule 1, 623–633, November 15, 2017

Figure 6. Ex Situ Raman Evidence for the Working Mechanism of Fe DESs
(A) The Raman spectra of 120- and 110-based Fe DESs.
(B–D) The Raman spectra of 210-based Fe DESs (B); the Raman spectra of original, discharged, and
charged (C) Fe(126) catholyte and (D) Fe(210) catholyte.

forming solvated ions such as [Fe(OD)6]3+ instead.27 For Fe(210) catholyte, shown in
Figure 6D, an obvious change could be observed at the discharging state that the
characteristic peaks of FeCl2$4H2O rather than FeCl3$6H2O (Figure S11B) occurred,
suggesting that [FeCl2(OD)4]+ reduced to be insoluble FeCl2$xH2O. During the
charging process, the solid FeCl2$xH2O was oxidized to reform [FeCl2(OD)4]+ and
the Raman spectrum recovered its original status. Figure S12 displays the chemical
titration using K3Fe(CN)6 and K4Fe(CN)6 solutions and physical changes of Fe(126)
and Fe(210) catholytes. The phenomenon is consistent with Raman and electro-
chemical results. The different coordination environments of Fe3+ in Fe(210) and
Fe(126) DESs result in different working mechanisms and will play an important
role in their respective electrochemical performance. Therefore, we propose a
new perspective for redox reactions in Fe-urea DESs:

Cathode reaction: [FeCl2(OD)4]+ + e / [FeCl2(OD)4] (Equation 6)

Cathode reaction: [FeCl4] + e / [FeCl4]2 (Equation 7)

Cathode reaction: [Fe(OD)6]3+ + e / [Fe(OD)5]2+ + OD, (Equation 8)

where [FeCl2(OD)4] appears to be a precipitate, causing the coagulation of Fe(210)

DES during discharging.

In conclusion, considering the results from Raman spectra and electrochemical tests,
we offer a new principle regarding Fe-urea DESs whereby the dissociation of

Joule 1, 623–633, November 15, 2017 631

[FeCl4] and [FeCl2(OD)4]+ by the EG additive, which can help avoid the formation of
solid, facilitates the full cycling performance, increases the utilization, and improves
reversibility. Following this principle, we obtained the preliminary result, as shown in
Figure S13. Dissociating the complex ions in Fe(210) DES, Fe(213) catholyte (3.6 M)
had the potential to reduce the charging/discharging potential gap and achieve the
stable cycling under full charge and discharge.

EXPERIMENTAL PROCEDURES
The details of DES preparation, cell assembly, and other characterizations are pro-
vided in Supplemental Experimental Procedures.

SUPPLEMENTAL INFORMATION
Supplemental Information includes Supplemental Experimental Procedures, 13 fig-
ures, and 1 table and can be found with this article online at https://doi.org/10.1016/
j.joule.2017.08.013.

AUTHOR CONTRIBUTIONS
L.Z., C.Z., and Y.D. contributed equally to this work. G.Y., L.Z., C.Z., and Y.D.
conceived the idea and designed the experiments. L.Z., C.Z., and Y.D. conducted
the experiments and data analysis. K.R.-M. assisted with some experiments and pa-
per editing. All authors co-wrote the manuscript and discussed the results.

ACKNOWLEDGMENTS
G.Y. acknowledges the financial support from the National Science Foundation
award (NSF-CMMI-1537894), Sloan Research Fellowship, and Camille Dreyfus
Teacher-Scholar award.

Received: May 6, 2017

Revised: July 12, 2017
Accepted: August 17, 2017
Published: October 11, 2017

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