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Li, Z. Ruan, Z. Tang, Z. Liu, Z. Wang, Y. Huang, Z. Pei, J. A. Zapien and C. Zhi, Energy Environ. Sci., 2018,
DOI: 10.1039/C8EE01415A.

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Initiating A Mild Aqueous Electrolyte Co3O4/Zn Battery with 2.2 V-

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High Voltage and 5000-Cycle Lifespan by a Co(III) Rich-electrode

Received 00th January 20xx, 1# 1# 1 1 1 1
Accepted 00th January 20xx Longtao Ma , Shengmei Chen , Hongfei Li , Zhaoheng Ruan , Zijie Tang , Zhuoxin Liu ,Zifeng
1 2 1 1 1, 3
Wang , Yan Huang , Zengxia Pei , Juan Antonio Zapien , Chunyi Zhi *
DOI: 10.1039/x0xx00000x
Zn/Co3O4 battery is one of the few aqueous electrolyte batteries with a potential >2 V voltage. Unfortunately, so far, all
www.rsc.org/
reported Zn/Co3O4 batteries are using alkaline electrolyte, resulting in a poor cycling stability and environmental problems.
Here, we report a Co(III) rich- Co3O4 nanorod material with vastly improved electrochemical kinetics. The Zn/Co(III) rich-
Co3O4 batteries can work well in ZnSO4 with CoSO4 additive aqueous solution as a mild electrolyte, delivering a high voltage
of 2.2 V, a capacity of 205 mAh∙g-1 (Co3O4) and an extreme cycling stability of 92% capacity retention even after 5000
cycles. Further mechanism study reveals a conversion reaction between in-situ formed CoO and Co3O4, which has never
been observed in an alkaline Zn/Co3O4 battery. Subsequently, a flexible solid-state battery is constructed and reveals high
flexibility and high energy density of 360.8 Wh∙Kg-1 at current density of 0.5 A∙g-1. Our research initiates the first Zn/Co3O4
battery working in a mild electrolyte, resulting in excellent electrochemical performance. It also indicates that the
electrochemical kinetics can be effectively enhanced by fine tuning atomic structure of electrode materials, opening a new
door to improve performances of aqueous electrolyte batteries.
Introduction irreversible discharged species, such as ZnO, Zn(OH)2, as well
12-14
The advanced energy storage technologies with low-cost and as the dendritic Zn-deposition and carbonate forming . The
high-safety warrant are required
1-4
due to the continuous second problem is the cycling stability, which is associated
demand to power portable electronics and electrified vehicles. with the adopted alkaline electrolyte and zinc ion storage
11, 15
Besides the widely used lithium ion batteries, zinc-based mechanism . In the alkaline systems, the zinc-based
batteries represent another one of the promising solutions to batteries are either non-rechargeable or poorly rechargeable
16-17
electrochemical energy-storage technologies with a high- (usually less than 500 cycles) . Even in recent, some mild
18-21 22
capacity zinc metal anode (819 mAh∙g-1) and high ion- electrolyte systems, including Zn-MnO2 , Zinc-H2V3O8 , Zn-
23-25 26
conductivity electrolyte (up to 1 S∙cm-1). The zinc metal V2O5 , Zn-VS2 were developed, the cycling stabilities are
electrode offers a low redox potential (about -0.76 V vs. stand still far from satisfactory to meet the expected demand (less
hydrogen electrode (SHE)) 5-6 and shows dramatic stability in than 2000 cycles). In 2016, Liu’s group achieved a
water resulting in a potentially large voltage window of zinc breakthrough in the aqueous zinc/manganese oxide battery of
ion batteries (> 2V) 7-8. super-long cycle life (up to 5000 cycles) with a new conversion
reaction mechanism adopted. However, the voltage is still
Currently, however, for the zinc-based batteries, a couple of conventionally low (about 1.4 V) which is the third challenge
challenges remain. The first one is the widely used alkaline 27
remains for the zinc battery systems . To sum up, a high-
electrolytes for the zinc-based batteries 9-11. For example, the voltage, environmentally friendly (mild electrolyte needed)
commercialized non-rechargeable batteries are based on the zinc battery with long cycling stability (mild electrolyte
Zn/MnO2 technology, which use the KOH based electrolyte. needed) has been long expected in the field.
The alkaline electrolytes are not environmentally friendly.
Even more important, the alkaline system generally results in Zinc-cobalt oxide battery is a less studied system among
poor rechargeability of the batteries due to the formation of various Zn batteries. So far, all reported zinc-cobalt oxide
batteries employ alkaline solution as electrolyte, resulting in
limited capacities at shallow depth of discharge, and poor
14, 28-29
cycling performance . The mild electrolyte can
effectively inhibit growth of Zn dendrites and potentially result
in a long cycling stability. In mild aqueous electrolyte
condition, the oxidation and reduction reactions of a zinc-
-
cobalt oxide battery could be interpreted as Co(III) + e ↔
Co(II) (1.83 V vs. SHE, resulting in a high theoretical voltage of
2.59 V). The preceding discussion suggests that the efficiency
of cobalt oxide as an electrode materials could be enhanced by

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increasing the population of Co(III) centers present at the attributed to the vibration of Co(III)-O coordination, where
oxide surface in mild condition. Therefore, the high- Co(III) ions are hexa-coordinated and filled in octahedral
2-
performance aqueous zinc-cobalt oxide battery is highly voids, in which O is cubic closely packed (Figure S3). It is

Energy & Environmental Science Accepted Manuscript

promising to be exploited by developing cobalt oxides with
high Co(III) content that is directly associate with the enhanced
electrochemical kinetics. However, it is difficult to use
individual Co(III)-O oxide in electrochemical devices due to
their instability under the operating conditions.
Herein, we firstly reported a highly reversible conversion
reaction in Zn/Co(III) rich-Co3O4 system. Different from all
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obviously observed that relative intensity of peak at 472.59
/peak at 517.28 increase to 0.98 compared to that of a well-
balanced Co3O4 (0.8) (Figure S4), indicating a high Co(III)
content in our synthesized Co3O4. The scanning electron
microscopy (SEM) image in Figure 1 c and d, exhibits a
homogeneous one-dimensional (1D) nanorod immobilized on
the CFC substrate. The length of Co3O4 nanorod extends to a

few micrometers with a diameter of around two hundred

previously reported Zn/Co3O4 batteries, the Zn/Co(III) rich-
nanometers. Intriguingly, several nanorods form a bundle with
Co3O4 system can work well in a mild aqueous electrolyte
a diameter of ~1 micrometer. Each nanorod is in fact
solution (2 M ZnSO4 +0.2 M CoSO4). Co(III) rich-Co3O4 is
composed of around 10 nm nanocrystal (Figure 1e and Figure
synthesized by introducing excess cobalt salt in synthesizing
S5). The sizes distribution of nanocrystals exhibits an average
process. Benefiting from the Co(III) rich structure and mild
size of 12 nm (Figure S5). The high-resolution transmission
electrolyte adopted, a high average voltage (~ 2.2 V), high
-1 -1 electron microscopy (HRTEM) image shown in Figure 1f is
specific capacity (205 mAh∙g at current density of 0.5 A∙g )
capable of resolving the lattice fringes of Co3O4 nanorod with a
and long-cycling lifespan (up to 5000 cycles with a capacity
lattice distance of 0.246 nm for the (311) crystal plane,
retention of 92 %), are simultaneously achieved. The
indicating that the as-synthesized spine Co3O4 is highly
electrochemical kinetics and performance of the Zn/Co(III) 30
crystalline and preferred orientation growth along [311] axis .
rich-Co3O4 system are thoroughly investigated. A reversible
The selected area diffraction (SAED) patterns of Co3O4 shown
conversion reaction mechanism between Co(III) rich-Co3O4
in Figure 1g are indexed to cubic spine crystalline,
nanorod and in-situ formed CoO layer was revealed during
corresponding to XRD results. The high-angle annular dark-
charge/discharge process, as confirmed by ex-situ Raman,
field transmission electron microscopy (HAAD-STEM)
transmission electron microscopy (TEM), X-ray diffraction
elemental mapping in Figure h-j shows that signals of cobalt
pattern (XRD) and X-Ray photoelectron spectroscopy (XPS)
and oxygen are well dispersed across the nanorods.
measurements. We further demonstrate a solid-state battery
that possesses a high flexibility and high energy density of To get insight into the Co(III) content of the as-synthesized
-1 -1
360.8 Wh∙Kg at a current density of 0.5 A∙g . Our work may Co3O4, the fine-scanned Co 2p XPS spectra of both well-
inspire a new approach to develop rechargeable aqueous balanced Co3O4 and Co(III) rich -Co3O4 were fitted to
batteries with high voltage, long-cycle life, and high capacity investigate the oxidation states of Co atoms with different
through fine tuning atomic structure of electrode materials. valences. It is obvious observed that through introduction of
3+ 2+
superfluous cobalt ions in precursor, the ratio of Co /Co in
Results and discussion Co3O4 nanorods dramatically increase from 0.998 to 1.696,
Preparation of rich Co(III)-Co3O4 nanorods indicating significantly more Co(III) presence in obtained Co3O4
nanorods (Figure 2a and b). Meanwhile, the characteristic
The Co(III) rich-Co3O4 nanorods immobilized on carbon cloth
peak of Co-O bond shifts (by 0.11 eV) to the high energy state
(CFC) are synthesized through hydrothermal method, followed
o and the increase of relative intensity of Co(III)-O/Co(II)-O in
by calcination at 350 C for 3 hours. The synthetic strategies
Raman spectra, further confirming the increase of Co(III)
are shown in Figure S1, involving two stages. In a typical
content in the synthesized Co3O4 nanorods (Figure S6). The
procedure, uniform nanorods (Figure S2) precursor grown on a
results will be in favor of high-voltage, high capacity aqueous
CFC is synthesized using urea, ammonium fluoride and excess
Zn/Co3O4 battery.
cobalt salt through hydrothermal routes and Co3O4 is obtained
through calcination. The introduction of excess cobalt salt in Electrochemical performance of Zn/Co(III ) rich-Co3O4 battery
precursor effectively promotes high Co(III) content in achieved
As shown in Figure 2c, the Co(III) rich-Co3O4 exhibits obvious
Co3O4. The X-ray diffraction (XRD) pattern shown in Figure 1a
charge/ discharge plateaus at about 2.1 and 2 V, respectively.
exhibits the crystalline phase of a cubic spinel-Co3O4 (JCPDS: -1
Moreover, it delivers a high capacity of 158 mAh∙g at current
43-1003) and no Co metal-related peaks observed. The broad -1
o density of 1 A∙g . Whereas the well-balanced Co3O4 shows
reflection peak at around 26 is assigned to CFC substrate
negligible charge/discharge plateaus with a low capacity of 91
whose intensity is significantly weaker than features of Co3O4, -1 -1
mAh∙g at 1 A∙g . The results confirm our assumption that
indicating that the Co3O4 nanorod is well spread on the
Co(III) content is key for electrochemical kinetics in a Zn/Co3O4
substrate. The Raman spectrum of Co3O4 can be assigned to
system in mild electrolyte. More interestingly, it was found the
the fundamental vibrational modes of Co3O4 with spinel
30 -1 Zn/Co(III ) rich-Co3O4 system works well in a mild aqueous
crystalline (Figure 1b). The peaks at 189.33 and 472.59 cm
ZnSO4 electrolyte with CoSO4 as additive and it is rechargeable.
are ascribed to the vibration of Co(II)-O coordination, where
It is a surprise as all up-to-now reported Zn/Co3O4 battery
Co(II) ions are tetra-coordinated and filled in tetrahedral
-1
interstices. The peaks at 517.28, 603.36 and 688.37 cm are

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must use alkaline electrolytes. In addition, the mild electrolyte provides a much better

Energy & Environmental Science Accepted Manuscript

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Figure 1. Structural and morphological characterization of Co(III) rich Co3O4 immobilized on carbon cloth: (a) X-ray diffraction
data, (b) Raman spectrum, (c, d) SEM images, (e) lattice fringes along (220) and (311) planes, (f) Electron diffraction ring, (g)
Crystal structure viewed along b axis and (h-j) STEM-HAADF image and STEM-EDS mapping of the elemental distribution of Co
(III) rich-Co3O4.

electrochemical performance than the conventional alkaline
electrolyte for the Zn/ Co(III) rich-Co3O4 system. The
electrochemical stability windows of Zn/rich Co(III)-Co3O4 in
the alkaline and mild aqueous electrolytes are evaluated using
cyclic voltammetry (CV) and galvanostatic charge/discharge
characterizations. The Zn/Co(III) rich-Co3O4 battery using a
mild aqueous electrolyte shows a voltage window of about 2.2
V, much broader than that of the battery with alkaline
electrolyte (about 1.9 V) (Figure 2d). The Co(III) rich-Co3O4
electrode start to produce oxygen from water splitting at 2.26
V (vs. Zn/Zn2+) in mild aqueous electrolyte, which is
significantly higher than that in alkaline medium (1.93 V) as
well (Figure S7). Thus, the electrochemical window of Zn/rich
Co(III)-Co3O4 batteries is up to 2.26 V. This observation unveils
the possibility to develop a high-voltage aqueous Zn/Co3O4
battery in mild aqueous medium. As shown in Figure 2e, the
Co(III) rich-Co3O4 nanorod electrode in the mild electrolyte,
2+
exhibits a high voltage of about 2.2 V versus Zn/Zn and a
-1
reversible capacity of 158 mAh∙g at a current density of 1 A∙g
1
. It is remarkably higher than that of Co3O4 in alkaline (1.9 V
-1
vs. Zn; capacity of 105 mAh∙g ), consistent with CV
measurements. The result is ascribed to different redox
reaction in cathode and anode electrode (Figure S8, to be
discussed shortly afterwards). Moreover, the battery using
mild aqueous electrolyte reveals a much better stability than
using alkaline medium (Figure 2f).
It should be noted that the CoSO4 additives is very important
for the above-mentioned electrochemistry. In the ZnSO4
aqueous electrolyte, Co dissolution and capacity fade occurs
during initial charge/discharge cycles, which is analyzed by the
change of Co concentration in electrolyte solution utilizing
inductively coupled plasma atomic emission spectrometer
(ICP-AES) (Figure S9). The amount of dissolved Co is up to 6.4
% of the total Co at the state of discharge to 0.8 V. The
dissolution of Co leads to the noticeable capacity loss in initial
cycles. Therefore, we believe that improvement of the cycling
stability of Zn/Co(III) rich-Co3O4 battery can be achieved by
pre-adding Co(II) ions to change the dissolution equilibrium of
Co(II) in Co3O4 electrode. The addition of Co(II) ions does not
-
change the redox

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Figure 2. High-resolution XPS spectra of Co 2p for (a) well-balanced Co3O4 and Co(III) rich-Co3O4. (c) Comparison of well-balanced
Co3O4 and Co(III) rich-Co3O4 cathode performance in 2M ZnSO4 with 0.2M CoSO4 additives electrolyte. Comparison of Zn/ Co(III)
rich-Co3O4 battery in 1M KOH and 2M ZnSO4 with 0.2M CoSO4 additives electrolyte: (d) CV curves, (e) Charge-discharge
polarization curves, (f) Stability test over initial 500 cycles at current density of 1 A∙g-1.

  , respectively. Moreover, when the rate
reaction. Moreover, the pre-addition of 0.2 M Co(II) into
electrolyte not only significantly improves the aqueous Zn/
Co(III) rich-Co3O4 battery to obtain long-term cycling stability
but also promotes to achieve high initial Coulombic efficiency
(Figure S10). The results manifest that the Zn/Co(III) rich-Co3O4
battery together with optimized mild electrolyte is really
promising for a high-voltage, long-lifespan, super-safety and
cost-effective energy storage technology.
The CV curves of Zn/Co(III) rich-Co3O4 battery in the optimized
2 M ZnSO4+0.2 M CoSO4 aqueous electrolyte at different scan
rates all shows a pair of redox peaks, which is ascribed to
conversion reaction between Co (III) and Co (II) (Figure 3a). It
corresponds to the plateau of charge/discharge shown in
Figure 3b. Moreover, the Zn/Co(III) rich-Co3O4 battery in mild
aqueous electrolyte exhibits a remarkable rate capability,
showing the discharge capacities of 200, 161, 146, 123, 105,
91, 83, 71, and 62 mAh∙g-1 recorded at rates of 0.5, 1, 2, 3, 4, 5,
6, 7, and 8 A∙
in Figure S12, under the alkaline condition, there is a sudden
shifted back to 0.5 A∙g-1, the capacity recovered to 200 mAh∙g-
1
, showing a strong tolerance to the high-speed conversion
reaction (Figure 3c). The excellent rate performance is
attributed to the stabilization and excellent electrochemical
kinetics of Co (III) rich-Co3O4 nanorod cathode. In addition, the
Zn/Co (III) rich-Co3O4 battery is galvanostatically charged-
discharged at 4 A∙g-1 to investigate the long-term cycle
stability. Obviously, the reversible capacity retains 110 mAh∙g-1
with a capacity retention of 92 % over even 5000 cycles and
the Coulombic efficiency maintains at 100% in all cycles (Figure
3d), which show absolute advantage compared to reported
aqueous batteries with less 2000 cycles (Table S1). In aqueous
ZnSO4+CoSO4 electrolyte, an increase of capacity is observed
within the initial several cycles, which is contributed to the
gradual activation process in the initial several cycles 26-27, 31.
The Co (III) rich-Co3O4 cathode remains the morphology of
nanorod after 5000 charge/discharge cycles, indicating
excellent structural stability of as-synthesized Co (III) rich-
Co3O4 electrode (Figure S11).
To probe the mechanism of the superior cycling stability
observed in the Zn/Co(III) rich-Co3O4 battery with
ZnSO4+CoSO4 mild electrolyte, a Zn/Zn symmetric battery in
alkaline and mild aqueous electrolyte is constructed. As shown
increase in polarization after 16 h after only eight cycles of Zn
stripping and plating (2 h per cycle), ascribing to the formation
of insulating ZnO powder layer to a critical thickness (Figure
S13 d-f), which is confirmed by XRD pattern in Figure S14. The
loose and powder-like Zn surface, which could deter the
cycling stability of Zn electrode. Whereas, in the mild aqueous

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electrolyte, neither dendritic morphology nor formation of structural evolution of the rich Co(III)-Co3O4. The CV curves are
byproducts (a dense and dendrite-free surface morphology as well repeated with cathodic peaks located at 2.2 V and an
shown in Figure S13 g-j) such as ZnO or Zn(OH)2 is evidenced overlapped anodic peak at 2.1 V (Figure S17). The discharge

Energy & Environmental Science Accepted Manuscript

after 280 h of repeated Zn stripping/plating test (Figure S14).
The same phenomenon is observed in the Zn/Co(III)-rich Co3O4
battery. The Zn anode in mild aqueous electrolyte reveals a
dense and dendrite-free surface morphology after 5000 cycling
stability tests (Figure S15), while ZnO nanosheets is obviously
observed when KOH electrolyte was used (Figure S16), which
eventually deter the stability of Zn anode. Therefore, the high-
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curve displays a flat plateau at around 2 V at a current density
-1
of 1 A∙g , in line with the CV results (Figure 4a). Ex-situ Raman
spectrum (Figure 4c) are recorded at the selected states
-
(marked points in Figure 4b). The peaks 472.59 and 517.28 cm
1
are typically ascribed to the vibration of Co(II)-O and Co(III)-O
coordination, respectively. During discharging process (A → D),
ratio of Co(III)-O/Co(II)-O decreases from 1.15 to 0.98, whereas

performance Zn/Co(III) rich-Co3O4 battery with ZnSO4+CoSO4
mild electrolyte, and especially the superior cycling stability, is
believed to arise from the vastly improved structural stability
of both Co(III) rich-Co3O4 and Zn electrode in the mild
electrolyte.
Chemical conversion reaction
The new mild electrolyte, together with the new Co(III) rich-
Co3O4 electrode may result in new energy storage mechanism.
The ex-situ TEM, XRD and Raman of rich Co(III)-Co3O4
nanorods cathode at initial and different charging-discharging
states are utilized to investigate the morphological and
in the following charging process (D → H), the strength ratio of
Co(III)-O/Co(II)-O increases from 0.98 to 1.15. It is attributed to
the reversible redox reaction between Co(III)-O and Co(II)-O.
This confirms the conversion reaction mechanism between
formed CoO and Co3O4 during discharge/charge process occurs
in Zn/Co(III) rich-Co3O4 batteries with mild electrolyte.
Moreover, the peak at around 680 cm-1 shifts to low
wavenumber in the Raman spectra during the discharge
process and then moves to high wavenumber to the original
condition upon charge process. This reversibility and gradual
shifting of the peak indicate the redox reaction associated with
Zn ions uptake/removal from Co3O4 lattice.

Figure 3. Electrochemical performance of Zn/Co(III) rich-Co3O4 batteries in 2M ZnSO4 aqueous electrolyte with 0.2M CoSO4
additives: (a) CV curves at different scanning rate, (b, c) Rate performance and (d) the long-term cyclic performance.

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The Co 2p core level spectra of Co(III) rich-Co3O4 at discharge new layer displays a crystalline structure with a lattice distance
(at 0.8 V) and charge (at 2.2 V) states shown in Figure 4c, d, are of 0.16 nm (Figure 5c), which is in agreement with the d space
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further used to verify the oxidation state of Co atoms during
3+ 2+
discharge/charge process. The ratio of Co /Co decreases
from 1.68 to 0.45 when the battery was discharged to 0.8 V
and it comes back to the original state (1.68) as charged to 2.2
V. The trend is consistent with the Raman analyses. In the O 1s
spectrum (Figure S18), the two binding energy peaks
corresponds to the characteristic bands of oxygen in the Co-O
32
lattice and surface bound water, respectively . When the
battery was discharged to 0.8 V, the characteristic peak of Co-
O shifts to a low binding energy, while being charged to 2.2 V,
it returned to the initial state (Figure S18). These results
further demonstrated the formation of CoO during discharging
and its conversion to Co3O4 during charging.
The observed morphological and structural evolution are
further investigated by ex-situ HR-TEM and SEM. The Co (III)
rich-Co3O4 nanorods retain original morphology during
discharge process to 0.8 V in the first cycle (Figure S19 a, b and
Figure 5a). Meanwhile, a newly thin layer is deposited on the
surface of nanorod (marked by white cycle) (Figure 5b). The
from the (220) lattice planes in face-centered cubic phase CoO,
as evidenced by the XRD pattern of the CoO phase formed
shown in Figure S20.The CoO layer formed in discharge
process is attributed to the high Co(III) content in active
materials of Co3O4, which has never been observed. The
formation of CoO layer reveals a possible conversion reaction
+
of H ions intercalation into Co (III) rich-Co3O4, which is in
consistence with Raman and XPS results. Therefore, we believe
+
that Co(III) rich-Co3O4 reacts with H ions from water to form
-
CoO. Meanwhile, the sequent OH ions interacts with ZnSO4
and H2O in the aqueous electrolyte to form a flake-like
ZnSO4[Zn(OH)2]3∙xH2O as shown in Figure S21 and reach a
27
neutral charge in the system . The structure of
ZnSO4[Zn(OH)2]3∙xH2O was confirmed by XRD pattern as shown
in Figure S22. The above conversion reaction is further
confirmed by the STEM-EDS mapping of the Co3O4 electrode in
the discharged state. The distribution of the elements Co, O
and Zn in Figure 5d reveals that the nanorods consist of O and
Co and Zn uniformly distributed.

Figure 4. Electrochemical and structural evolution of Co(III) rich-Co3O4 during electrochemical process: (a) Typical
-1
charge/discharge curves for the second cycles at current density of 1 A∙g in 2M ZnSO4 aqueous electrolyte with 0.2M CoSO4
additives. The points A-H marked the state where are collected for Raman analysis. (b) Ex-situ Raman spectrum of Co3O4 cathode
at selected state during the second cycles. High-resolution XPS spectrum of Co 2p for (c) discharge to 0.8 V and (d) following
charge to 2.2 V.

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2+ -1
When the Zn/Co(III) rich-Co3O4 battery is charged to 2.2 V, the Zn + 2OH + ZnSO4 + xH2O ↔ ZnSO4∙[Zn(OH)2]3∙xH2O
CoO layer change back to the original Co(III) rich-Co3O4 2+ -
Anode: Zn ↔ Zn + 2e
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through oxidation reaction (Figure S12 c, d and Figure 5e). The

result can be confirmed by the lattice distance of 0.265 nm, Overall: Co3O4 + Zn + (x/3) H2O + (1/3) ZnSO4 ↔ 3CoO + (1/3)
corresponding to (311) crystal plane of spine-Co3O4, which ZnSO4∙[Zn(OH)2]3∙(x-1) H2O
manifest a reversible structure change during
Based on analysis, the reaction in cathode and anode in mild
charge/discharge process (Figure 5f, g). This observation is
electrolyte is significantly different from that in alkaline
consistent with the reversible charge/discharge behaviors of - -
condition (cathode: Co3O4 + OH + H2O↔ 3CoOOH + e ; anode:
Zn/Co (III) rich-Co3O4 aqueous batteries shown in Raman, XPS 2- - -
2[Zn(OH) ] + 4e ↔ 2Zn + 8OH ) (Figure S8). The results lead to
and XRD characterization.
a lower voltage of 1.9 V and poor cycling stability due to the
- -
To conclude, the electrochemical reaction of the Zn/Co(III) irreversible reaction of Zn + 2OH → Zn(OH)2 + 2e → ZnO +
rich-Co3O4 battery with ZnSO4-CoSO4 mild electrolyte can be H2O. In contrast, in mild 2 M ZnSO4 + 0.2 M CoSO4 aqueous
summarized as below: electrolyte, the combination of a highly reversible Zn anode
+ -1 and a Co (III) rich-Co3O4 nanorod cathode exhibits a high
Cathode: H2O ↔ H + OH
voltage of 2.2 V, and high cycling stability of 5000 cycles with
+ -
Co3O4 + 2H + e ↔ 3CoO + H2O 92 % capacity retention, which is also both environmentally
benign and safe.

Figure 5. Morphology characterization of Co3O4 during electrochemical process: (a-c) Co (III) rich-Co3O4 anode discharge to 0.8V
and then (e-g) charge to 2.2V in the first cycle. (d) STEM-HAADF image of and STEM-EDS mapping of the elemental distribution of
Co, O and Zn in the Co (III) rich-Co3O4 anode in the discharged state during the first cycle. Electrolyte: 2M ZnSO4 aqueous
electrolyte with 0.2M CoSO4 additives.

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Journal Name

Energy & Environmental Science Accepted Manuscript

ARTICLE

Solid-state device. under normal and different deformation condition is

investigated using CV and galvanostaticly charging-discharging
Building on the exceptional performance of rechargeable
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characterization. The CV at different sweep rates within the

aqueous Zn/Co (III) rich-Co3O4 battery, the solid-state
rechargeable Zn/Co(III) rich-Co3O4 battery is facilely assembled
in an open-air environment with sandwich structure (Figure
6a). Notably, the process of assembling solid-state Zn/Co(III)
rich-Co3O4 battery does not require water-free and oxygen-
free environment, in favor of scaling up. In detail, as shown in
Figure S23, the freestanding deposited-Zn on carbon cloth
(Figure S24, 25) is used as anode, freestanding Co3O4 on
carbon cloth as cathode and a polyacrylamide (PAM) hydrogel
as electrolyte. The freeze-dried PAM hydrogel possesses a
mass of interconnected macro-pores (Figure S26), which
allows ions to transfer freely and adequately in the
33
electrolyte . The ion conductivity of the PAM electrolyte is
evaluated using electrochemical impedance spectroscopy (EIS)
(Figure S27). The ionic conductivity enhances with increase of
-1
swelling ratio and is up to maximum value of 0.12 S∙cm at 300
% swelling ratio (Figure S28). Thus, it can serve as superior
ionic conductor for solid-state electrolyte used in solid-state
Zn/ Co(III) rich-Co3O4 battery system. The electrochemical
performance of the solid-state Zn/Co(III) rich-Co3O4 battery
2+
potential range of 0.8-2.3 V (vs. Zn/Zn ) show a pair of redox
peaks, which is ascribed to the conversion reaction of Co (III)
and Co (II), consistent with that in aqueous electrolyte system
(Figure 6b). Interestingly, the solid-state Zn/Co(III) rich-Co3O4
battery shows superior rate capability even at a high current
-1 -1
density of 8 A∙g with capacity of 52 mAh∙g . After cycling at
-1
current densities as high as 8 A∙g , an average discharge
-1
capacity of 178.6 mAh∙g is still recovered at a current density
-1
of 0.5 A∙g , equivalent to 98.9% of the initial average capacity
-1
(180.6 mAh∙g ) (Figure 6c). This is attributed to the good ion
conductive capability of the PAM hydrogel electrolyte, due to
the highly porous network to allow fast kinetic in the process
of charge-discharge. Meanwhile, the solid-state Zn/Co(III) rich-
Co3O4 battery exhibits remarkable long-term cycling stability.
The capacity retains 94.6%, even after 2000 cycles at a large
-1
current density of 2 A∙g (Figure 6d). This noticeable long-term
cycle performance is mainly assigned to the superior reactivity
and interfacial durability between PAM hydrogel electrolyte
and electrode, and superior water holding capability to
immobilize substantive aqueous electrolyte in matrix.

Figure 6. Electrochemical performance of solid-state Zn/Co(III) rich-Co3O4 batteries with Co(III) rich-Co3O4 nanorod on carbon
cloth as cathode, deposited Zn on carbon cloth as anode, and polyacrylamide (PAM) hydrogel as electrolyte: (a) Schematic
illustration of the structure of solid-sate Zn/Co(III) rich-Co3O4 batteries. (b) CV curves at different scan rate, (c) Rate performance,
(d) Stability of long-term cyclic performance, (e) electrochemical performance at different bending degree and (f) single battery
to power digital watch and two batteries connected in series to power electroluminescent panel (size: 12*3 cm) under different
bending condition.

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The high robustness, excellent durability and sensational
elasticity of the battery under various deformation conditions
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are critical for flexible/wearable devices in practical
34,35
application . Fulfilling the wearable battery applied for
portable electronics, our solid-state Zn/Co (III) rich-Co3O4
battery exhibits excellent flexibilities. The flexible/wearable
Zn/Co(III) rich-Co3O4 battery is evaluated under different
deformation condition and a continuous deformation tests. It
can be observed that the capacity remains almost unchanged
-1
at a current density of 1 A∙g under different deformation
conditions (Figure 6e). Moreover, a negligible capacity loss was
obtained after our solid-state Zn/Co(III) rich-Co3O4 battery
o
distorted at a bending angle of 90 for 1000 times utilizing an
especially designed stepper motor (Figure S29), exhibiting a
high mechanical durability of the flexible Zn/Co(III) rich-Co3O4
battery. It is due to the mechanical robustness of freestanding
Co(III) rich-Co3O4 on carbon cloth (Figure S30) and deposited
Zn on carbon cloth (Figure S31). The Co(III) rich-Co3O4
nanorods and deposited Zn are firmly on the carbon cloth after
being bent under different angle or after being bent many
times. In addition, multiple batteries can be integrated in
parallel or series to enlarge the output current and voltage,
respectively. Single battery with an voltage of ~2.2 V, can
power a digital watch (Figure 6f) and two batteries connected
in series can achieve an output voltage of ~4.4 V with similar
discharge time of a single battery (Figure S32), which can be
used to power a 36 cm2 flexible electroluminescent panel
(Figure 6f). By connecting two batteries in parallel, the
discharge time of the assembly is about twice that of a single
device when being discharged at the same current density.
Thus, our solid-state Zn/Co3O4 battery as a reliable and
powerful energy storage system can be used potentially in
various practical applications.
Conclusions
To overcome the stubborn problem that Zn/Co3O4 battery can
only work in alkaline electrolyte, we successfully fabricated
Co(III) rich-Co3O4 nanorods through introduction of
superfluous cobalt ions in a hydrothermal process. The Co(III)
rich-Co3O4 works well in an optimized mild 2 M ZnSO4+ 0.2 M
CoSO4 electrolyte, in which the CoSO4 were used as additives
to suppress the Co(II) dissolution. Benefiting from improved
electrochemical kinetics of Co(III) rich-Co3O4 cathode,
optimized mild electrolyte and highly stable Zn anode in mild
electrolyte, the Zn/Co(III) rich-Co3O4 battery delivers an
extremely good cycling stability: 92% capacity retention even
after 5000 cycles, together with a high voltage of 2.2 V and a
high rate capacity. Further mechanism study reveals a highly
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Energy & Environmental Science Accepted Manuscript
reversible conversion reaction between the formed CoO and
Co3O4. Notably, it is the high content of Co(III) in the Co(III)
rich-Co3O4 leads to highly effective redox reaction.
Furthermore, the freestanding cathode of Co(III) rich-Co3O4
nanorod on CFC based solid-state battery displays excellent
superior flexibility and robustness with the superior
electrochemical performances kept, exhibiting potential to
wearable applications. Our research successfully breaks the
Zn/Co3O4 battery away from the notorious environmentally
non-friendly alkaline electrolytes and simultaneously achieves
extremely good cycling stability, high voltage and high capacity
in a mild aqueous electrolyte battery system. Moreover, we
demonstrated that fine tuning atomic structure of electrode
may result in different electrochemistry, which may create
more opportunities in battery research.
Acknowledgements
This research was supported by NSFC/RGC Joint Research
Scheme under Project N_CityU123/15 and City University of
Hong Kong (PJ7004645). The work was also partially sponsored
by the project 2017JY0088 supported by Science & Technology
Department of Sichuan Province and was partially supported
by the Chengdu Research Institute (2017JY0088), City
University of Hong Kong (9610372).
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Broader context

Energy & Environmental Science Accepted Manuscript

Advanced energy-storage technologies with low-cost and high-safety warrant are the key

factors of next-generation electronics. Aqueous zinc-cobalt oxide batteries may offer ideal

solution to various challenges in this field, benefiting from their high safety and low-cost
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electrolyte with high ion-conductivity, high capacity of zinc metal electrode and potentially

large voltage window. Unfortunately, so far, all reported zinc-cobalt oxide batteries can only

work with alkaline electrolyte, leading to a poor cycling stability and environmental problems.

Our work presents a highly reversible conversion reaction in zinc-cobalt oxide system

enabled by a Co(III) rich-electrode, which initiates a mild aqueous electrolyte Co3O4/Zn

battery with 2.2 V-high voltage and 5000-cycle lifespan. A flexible solid-state battery is then

designed based on the developed material, which reveals high flexibility, high energy density

and superior safety performance. Our research demonstrates that fine tuning atomic structure

of electrode may effectively promote kinetics in electrochemical reactions. In addition, the

demonstrated flexible devices exhibit vast potentials for wearable electronics.

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Energy & Environmental Science Accepted Manuscript

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Rechargeable aqueous zinc-cobalt oxide batteries with high voltage, excellent rate capability and
long-cycling life.