ARTICLES

PUBLISHED: 18 APRIL 2016 | ARTICLE NUMBER: 16039 | DOI: 10.1038/NENERGY.2016.39

Reversible aqueous zinc/manganese oxide energy

storage from conversion reactions
Huilin Pan1, Yuyan Shao1*, Pengfei Yan2, Yingwen Cheng1, Kee Sung Han2, Zimin Nie1,
Chongmin Wang2, Jihui Yang3, Xiaolin Li1, Priyanka Bhattacharya1, Karl T. Mueller4,5 and Jun Liu1*

Rechargeable aqueous batteries such as alkaline zinc/manganese oxide batteries are highly desirable for large-scale energy
storage owing to their low cost and high safety; however, cycling stability is a major issue for their applications. Here we
demonstrate a highly reversible zinc/manganese oxide system in which optimal mild aqueous ZnSO4 -based solution is used
as the electrolyte, and nanofibres of a manganese oxide phase, α-MnO2 , are used as the cathode. We show that a chemical
conversion reaction mechanism between α-MnO2 and H+ is mainly responsible for the good performance of the system. This
includes an operating voltage of 1.44 V, a capacity of 285 mAh g−1 (MnO2 ), and capacity retention of 92% over 5,000 cycles.
The Zn metal anode also shows high stability. This finding opens new opportunities for the development of low-cost, high-
performance rechargeable aqueous batteries.

E
nergy storage is critical for renewable integration and
electrification of the energy infrastructure1–8 . Many types
of rechargeable battery technologies are being developed.
Examples include traditional lead-acid batteries based on
conversion reactions and Li-ion batteries based on intercalation.
Although today’s Li-ion batteries have high energy density, it is still
expensive to scale up. On the other hand, lead-acid batteries are
low-cost aqueous systems and much easier to scale up for stationary
applications. Nevertheless, the use of lead causes significant
environmental concerns besides the low energy density and limited
life span, even though lead-acid batteries still account for more than
half of the global battery market. An alternative, low-cost aqueous
energy storage system is highly desirable9–11 .
So far, a variety of aqueous batteries using alkaline cations,
for example, Li+ , Na+ , K+ , Mg2+ and/or mixed metal ions, as
charge carriers have been reported in the literature12–16 . Recently,
a new concept—aqueous Zn ion batteries—has been studied using
a high-capacity Zn metal anode (819 mAh g−1 ), whereas most
previous studies focused on Zn ion intercalation mechanisms and
showed limited long-cycle stability17 . A family of Prussian blue
analogues has lately been reported as zinc intercalation cathodes
in Zn ion batteries. However, these cathodes deliver limited
capacities (around 50 mAh g−1 ) and suffer O2 evolution due to
the high operating voltage (about 1.7 V versus Zn)18,19 . Recently,
alkaline Zn/MnO2 batteries have been shown to be rechargeable for
extended cycles using a shallow cycling protocol (typically no more
than 0.2–0.5 e− per 1 mol MnO2 )20,21 . Meanwhile, fully cycled (1 e−
per 1 mol MnO2 ) rechargeable Zn/MnO2 cells have been studied
using α-, γ-phase, or amorphous MnO2 as the cathode in mild
aqueous electrolytes22–24 . The MnO2 cathode suffers significant
capacity fading during roughly the initial 20 cycles25–27 . These
studies also focus on Zn2+ ion intercalation in the MnO2 framework
as the main charge storage mechanism. Several types of intercalation
products through two-phase or a series of complex single- and
two-phase reactions have been claimed, for example, spinel
ZnMn2 O4 22,25,28 , tunnel-type Znx Mn2 O4 24 , layered birnessite26 ,
layered Zn-buserite, and/or their complex composite24,29 . Also,
Mn K-edge X-ray absorption spectra of Zn/MnO2 show evidence
only for the redox reaction of Mn during charge/discharge24,26,27 .
However, the reaction mechanism involved remains a topic
of discussion.
Herein, we demonstrate a highly reversible conversion reaction
in aqueous Zn/MnO2 systems using α-MnO2 nanofibres as the
cathode. High capacity and high reversibility can be achieved over
5,000 cycles, with a capacity retention of 92%. The morphological
and structural evolution of a MnO2 nanofibre cathode were
carefully investigated during electrochemical reactions by means
of transmission electron microscopy (TEM), scanning TEM/energy
dispersive spectroscopy (STEM–EDS) mapping coupled with X-ray
diffraction (XRD) methods, and nuclear magnetic resonance
(NMR) spectroscopy to reveal the conversion reaction processes.
The Zn anode has also been examined carefully. This study provides
insights necessary to address the challenges faced in the practical use
of the Zn/MnO2 system for energy storage.
Electrochemical performance of Zn/MnO2 batteries
α-MnO2 nanofibres were synthesized with a hydrothermal method
and used as the cathode in a Zn/MnO2 battery chemistry study.
The XRD pattern in Fig. 1a shows the crystalline phase of α-MnO2
(JCPDS: 44-0141). The TEM image in Fig. 1b shows a homogeneous
one-dimensional (1D) nanofibre structure of α-MnO2 . The length
of α-MnO2 nanofibre extends to a few micrometres, with a
diameter of about 50 nm. The inset in Fig. 1b shows high-resolution
transmission electron microscopy (HRTEM) images, capable of
resolving the lattice, of 1D α-MnO2 nanofibres with a lattice distance
of 0.345 nm for the (220) crystal plane. This indicates that the as-
prepared α-MnO2 is highly crystalline, with the [220] axis as the
preferred orientation for 1D fibres30 .

1
Energy & Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, USA. 2 Environmental Molecular Sciences
Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352, USA. 3 Department of Materials Science & Engineering, University of
Washington, Seattle, Washington 98195, USA. 4 Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland,
Washington 99352, USA. 5 Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, USA.
*e-mail: yuyan.shao@pnnl.gov; jun.liu@pnnl.gov

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ARTICLES NATURE ENERGY DOI: 10.1038/NENERGY.2016.39

a b

(220)
0.345 nm

10 20 30 40 50 60 70 80
2θ (°) 500 nm

Figure 1 | Structural and morphological characterization of MnO2 . a,b, X-ray diffraction data (a) and TEM image (b) for α-MnO2 nanofibres. The inset of b
shows lattice fringes along the (220) planes.

b 270 270
a

Capacity (mAh g−1)

180 180
1.75

90 90
0 10 20 30
Voltage (V) versus Zn

1.50 0
300 mV 0 100 200 300 400
Cycles
c
60 120

Equivalent capacity
1.25
Zn/Mn mole ratio

loss (mAh g−1)

100
45
First 80
1.00 Second

0 70 140 210 280 30 60

0 5 10 15 20 25
Capacity (mAh g−1)
Cycles

Figure 2 | Electrochemical behaviours of Zn/MnO2 batteries with 2 M ZnSO4 as electrolyte. a,b, Charge/discharge curves of a Zn/MnO2 battery in the
initial two cycles (a) and cycling performance at C/5 (b) of the cell with 2 M ZnSO4 electrolyte (1C = 308 mAh g−1 , capacity is based on the mass of
MnO2 ). The inset in b is an enlargement of the cyclic data during the initial cycles. c, Elemental analysis of dissolved Mn2+ ions in the aqueous electrolyte
during cycling (the red and blue dot lines correspond to the mole ratio between Zn2+ and Mn2+ ions in the electrolyte and the equivalent capacity loss on
cycling, respectively).

In contrast to the conventional primary alkaline MnO2 battery31 ,
a mild aqueous ZnSO4 electrolyte was used for the rechargeable
Zn/MnO2 battery in this work. Figure 2a shows that α-MnO2
nanofibre exhibits an average operating voltage of about 1.44 V
versus Zn and reversible capacities of 210 and 255 mAh g− 1
MnO2
at C/5
in the initial two cycles, respectively—higher than the previously
reported values22,26 . It is interesting that the Zn/MnO2 battery shows
rather different charge/discharge curves for the initial two cycles,
and a nontrivial overpotential of about 300 mV (C/5) in the initial
cycle, which are rarely seen in intercalation electrode materials32 —
this will be discussed in depth later (note: there is still a overpotential
gap of about 200 mV even at C/100). The total overpotential is taken
roughly as the voltage difference between charge and discharge
at the midpoint of the voltage profiles (Supplementary Fig. 1).
Although a high reversible capacity can be delivered in the first
two cycles, a rapid deterioration in capacity was observed for the
Zn/MnO2 battery upon cycling (Fig. 2b). We ascribed this capacity
fading to the dissolution of Mn2+ from Mn3+ disproportionation into
the electrolyte during cycling. This is confirmed by an analysis of
the Mn concentration (measured by the inductively coupled plasma
(ICP) technique) in the electrolyte solution (Fig. 2c). However, the
increase in content of dissolved Mn2+ ions slows down after the
initial ten cycles (Fig. 2c). This is probably because the Mn2+ ions
gradually dissolved in the electrolyte change the equilibrium of Mn
dissolution from the MnO2 electrode, and thus suppress significant
continuous Mn2+ dissolution. This process is consistent with the
reduced trend in capacity fading in the following cycles (Fig. 2b).
Finally, a probable self-stabilization in capacity was observed over
hundreds of cycles as a result of the natural dissolution of MnO2 ,
but this takes extended cycling and suffers a significant capacity
loss (Fig. 2b).
On the basis of the above observation, we pre-added Mn2+
ions into the electrolyte to change the dissolution equilibrium
of Mn2+ from the MnO2 electrodes, and thus stabilize the
electrodes themselves. Figure 3a shows cyclic voltammetry (CV)
curves of Zn/MnO2 batteries in electrolytes, with and without
MnSO4 , revealing a similar redox behaviour that indicates the
MnSO4 additive did not affect the redox reactions in the MnO2

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NATURE ENERGY DOI: 10.1038/NENERGY.2016.39 ARTICLES
a 800 b 320
No additive C/3
With MnSO4 additive 1C

240
400

Capacity (mAh g−1)

Current (µA)

160 No additive
0.1 M MnSO4 additive
0

80

−400

0
1.00 1.25 1.50 1.75 2.00 0 15 30 45 60
Voltage (V) versus Zn Cycles

c d
100
1.8
100

Coulombic efficiency (%)

Capacity retention (%)
Voltage (V) versus Zn

1.6 5C 92% 75
75

1.4
50
50

1.2

25 25
1.0
10C 5C 2C 1C
0 0
0 70 140 210 280 0 1,000 2,000 3,000 4,000 5,000
Capacity (mAh g−1) Cycles

Figure 3 | Improved electrochemical performance of Zn/MnO2 batteries in optimal aqueous electrolyte. a,b, Comparison of CV scanning (0.1 mV s−1 ,
second cycle) (a) and the cycling performance (b) of MnO2 electrodes with and without 0.1 M MnSO4 additive in a 2 M ZnSO4 aqueous electrolyte at C/3
and 1C, respectively. c,d, Rate performance (c) and the long-term cyclic performance (d) of a Zn/MnO2 battery using an electrolyte with a MnSO4 additive.

electrodes. The two pairs of redox peaks are consistent with the
two plateaux in the charge/discharge curves shown in Fig. 2a.
However, with the MnSO4 additive in the electrolyte, the cycling
performance of the MnO2 electrode is significantly improved
(Fig. 3b). It is highly likely that pre-addition of 0.1 M Mn2+
will provide an appropriate equilibrium between Mn2+ dissolution
(from the electrode to the electrolyte, as shown in Fig. 1c)
and the re-oxidation of Mn2+ in the electrolyte, leading to high
stability of the electrode. Pre-addition of Mn2+ above or below
the equilibrium amount does not address the capacity fading
issue well (see detailed dissolution in Supplementary Discussion 1:
Dissolution/oxidation of Mn2+ /MnO2 reactions). Adding MnSO4 to
the electrolyte also greatly improves the utilization of MnO2 active
material, delivering a higher capacity than that without MnSO4 .
Decent capacities of 285 and 260 mAh g− 1
MnO2
were delivered for
cells at current rates of C/3 and 1C, respectively, higher than
previously reported values33 . Moreover, the Zn/MnO2 battery with
the MnSO4 additive shows an excellent rate capability, achieving
−1
high capacities of 207, 161 and 113 mAh gMnO at 2C, 5C and 10C,
respectively (Fig. 3c). The high rate performance could be ascribed
to the stabilization and excellent kinetics of the MnO2 electrodes
and the Zn anodes (to be discussed below)34–36 . Furthermore, the
Zn/MnO2 battery with the MnSO4 additive also exhibits excellent
long-cycle stability, with a high-capacity retention of 92% after
5,000 cycles at a rate of 5C (Fig. 3d). This indicates that a
Zn/MnO2 system using a mild aqueous electrolyte is very promising
for a high-performance, long-life, environmentally-friendly, cost-
effective energy storage solution.
Chemical conversion reaction
TEM was used to investigate the morphological and structural
evolution of α-MnO2 electrodes during charge/discharge
in Zn/MnO2 aqueous batteries. Figure 4a shows that the
α-MnO2 electrode underwent marked changes in morphology
when discharged to 1 V in the first cycle. Pristine well-defined
micrometre-long nanofibres were transformed to short nanorods
and nanoparticle aggregates (marked by yellow and blue rectangles
respectively). HRTEM was used to characterize the structural
change, as shown in Fig. 4b,c. Short nanorods predominantly
exhibit a crystalline structure with a lattice distance of 0.33 nm and
some disordered regions (Fig. 4b). The short nanorods are a newly
formed discharge product different from the pristine α-MnO2 , as
can be seen from the difference in the crystalline orientation (arrow
indicates the extension outline of the nanorod). In addition, the
nanoparticle aggregates in the discharged state consist of ∼5 nm
particles with a uniform lattice distance of 0.26 nm, as characterized
in Fig. 4c. It was previously reported that Zn2+ ions intercalate
2
into α-MnO2 to form spinel ZnMn2 O4 , or a tunnel or layered
Znx MnO2 phase22,24,26 . However, our TEM results showed that the
lattice fringes of 0.33 and 0.26 nm from the discharged products
do not match the reported intercalated phases in the literature.
In fact, they are consistent with the d spaces from the (210) and
(020) planes in monoclinic MnOOH, as evidenced by the XRD
patterns of the MnOOH phase formed shown in Supplementary
Fig. 2. The formation of MnOOH indicates a possible, alternative
conversion reaction to Zn2+ ion intercalation into MnO2 . It is
very likely that MnO2 reacts with a proton from water to form

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ARTICLES NATURE ENERGY DOI: 10.1038/NENERGY.2016.39

a b c d

0.26 nm

0.33 nm
Nanorod 0.26 nm STEM-HAADF

Nanoparticle 0.26 nm
aggregates

0.26 nm
Disordered
200 nm 5 nm zone 5 nm
Mn

e f g

Nanorod

0.34 nm
(220) α-MnO2 O

Nanoparticle
aggregates

100 nm 5 nm 5 nm
Zn

Figure 4 | TEM/HRTEM images of MnO2 electrodes during electrochemical process. a–c,e–g, MnO2 electrodes discharged to 1 V (a–c) and then charged
back to 1.8 V in the first cycle (e–g). The yellow and blue rectangular regions have a morphology typical for short nanorods and nanoparticle aggregates,
respectively. The arrows in b and f indicate the growth directions of the short nanorods. d, STEM-HAADF image of short nanorods and STEM–EDS
mappings of the elemental distributions of Mn, O and Zn in the MnO2 electrode in the discharged state during the first cycle. Electrolyte, 2 M ZnSO4
aqueous electrolyte with 0.1 M MnSO4 additive.

MnOOH (MnO2 + H+ + e− ↔MnOOH). Interestingly, whereas
the H+ ions react with MnO2 , the sequent OH− ions react with
ZnSO4 and H2 O in the aqueous electrolyte to form a large flake-like
ZnSO4 [Zn(OH)2 ]3 · xH2 O and reach a neutral charge in the
system. This reaction product was not stable under the high-energy
electron beam of TEM, but is clearly confirmed in the strong
XRD signal (Supplementary Fig. 3a), which dominated the XRD
patterns of other phases, for example, α-MnO2 , and MnOOH, as
shown in Supplementary Fig. 2. This reaction was also supported
by the 1 H NMR study in Supplementary Fig. 4, which confirms
the formation of ZnSO4 [Zn(OH)2 ]3 · xH2 O after discharge. The
above conversion reaction is further confirmed by the STEM–EDS
mapping of the MnO2 electrode in the discharged state. Comparing
the distribution of the elements Mn, O and Zn in Fig. 4d reveals that
the short nanorods and nanoparticles consist of O and Mn, and no
evidence of Zn (note: H atoms cannot be detected in STEM–EDS
mapping). In contrast, Zn is mainly distributed on the flake-like
solid, that is, ZnSO4 [Zn(OH)2 ]3 · xH2 O, as confirmed by the TEM
and STEM–EDS mapping in Supplementary Fig. 3b,c. Different
from previous reports of Zn interaction into MnO2 , both TEM
and STEM–EDS mapping evidently confirm the above conversion
reaction to form MnOOH. (The background of the Zn mapping
results from associated side products during the formation of
MnOOH on the cathode.) The reaction mechanism of the active
conversion reaction between MnO2 and H+ is further confirmed
by the fact that only very limited capacity (capacitor behaviour)
can be delivered in organic Zn2+ -ion-based electrolytes owing to
the absence of H+ ions in organic electrolytes (note: the Zn anode
functions well in an organic electrolyte, as seen from the reversible
stripping/plating of Zn in Supplementary Fig. 5a). After adding
H2 O into organic Zn-based electrolytes, the Zn/α-MnO2 battery
exhibits a similar electrochemical behaviour to that in an aqueous
electrolyte (Supplementary Fig. 5b).
For the charged state, the short nanorods mainly retain their
morphology, whereas both the lattice distance and crystallinity
revert to those of the original α-MnO2 electrode, which implies
a reversible structure change (Fig. 4d,e). This is consistent with
the reversible charge/discharge behaviours of Zn/MnO2 aqueous
batteries shown above. The nanoparticle aggregations also show
a similar morphology after charging back as they do in the
discharged state. At the same time, the consequent formation of
ZnSO4 [Zn(OH)2 ]3 · xH2 O on the cathode side is also reversible
and stable with the hydrogenation/dehydrogenation of the MnO2
cathode (Supplementary Fig. 3a,d).
As discussed above, the structure/morphology of α-MnO2
evolves from original micrometre-long nanofibres to a well-mixed
composite of short nanorods and nanoparticle aggregations after the
initial cycle, which stabilizes and enhances the structural mechanics
and kinetics of the electrodes by releasing strain and reducing
the diffusion length for ions and electrons in the nanocomposite
structure, resulting in the excellent rate and cycling stability of
the Zn/MnO2 aqueous batteries. In addition, the evolution of the
morphology from the original α-MnO2 micro-nanofibres to short
nanorods and nanoparticle aggregations adds extra surface energy
to the Gibbs free energy of the α-MnO2 electrode after charging, in
comparison to that of the original α-MnO2 fibres; this accounts for
the voltage difference between first discharge and second discharge
as shown in Fig. 2a (see detailed explanation in Supplementary
Discussion). This phenomenon of a voltage difference in the first
two cycles has also been observed and discussed in other conver-
sion reactions from metal oxides electrode materials in lithium-
and sodium-ion batteries37–39 . Furthermore, such thermodynamic
factors, for example, the volume and surface energy variations dur-
ing electrochemical processes in the present MnO2 cathode, also
account for the existence of a total overpotential of ∼200 mV in
the MnO2 electrodes even at a zero-current density (Supplementary

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NATURE ENERGY DOI: 10.1038/NENERGY.2016.39 ARTICLES
a 40% KOH 2 M ZnSO4 + 0.1 M MnSO4 b

Zn in 40% KOH Zn in ZnSO4 Zn in ZnSO4

12 h 12 h 400+ h
2 Increase in
polarization

5 µm
Voltage (V)

0
0.06
0.24 mA cm−2 0.48 mA cm−2 0.72 mA cm−2 c 342 Zn
0.03 228
−1
Voltage (V)

±38 mV ±35 mV ±35 mV 114

0.00 Zn
O S
0
2 4 6 8 10
−0.03 Energy (keV)
−2

−0.06
0 40 80 120 160 200 240
Time (h)
−3
0 5 10 15 60 120 180 240 5 µm

Test time (h)

Figure 5 | Characterization of Zn anode electrodes. a, Zn stripping/plating from Zn/Zn symmetrical cells at 0.24 mA cm−2 in a 40 wt% alkaline
electrolyte and at 0.24–0.72 mA cm−2 in a mild 2 M ZnSO4 with 0.1 M MnSO4 aqueous electrolyte, respectively. The stripping/plating capacities of the Zn
electrodes (1.25 cm2 ) are 0.3, 0.6 and 0.9 mAh in each cycle. The inset of a shows optical images of cycled Zn anodes in alkaline and mild aqueous
electrolytes. b, SEM image of a pristine Zn anode. c, SEM image and EDX spectrum (inset) of a Zn anode after 120 cycles (240 h) in 2 M ZnSO4 with 0.1 M
MnSO4 aqueous electrolyte.

Fig. 6). This phenomenon is consistent with the significant voltage The reactions of the rechargeable aqueous Zn/MnO2 chemistry
hysteresis of Zn/MnO2 batteries—that is, ∼200 mV of voltage hys- can be formulated as below:
teresis even at C/100 (Supplementary Fig. 1)38 .
Cathode: H2 O ↔ H+ + OH−
MnO2 + H+ + e− ↔ MnOOH
Zn anode 1
Zn2+ + OH− + 16 ZnSO4 + x6 H2 O ↔
The Zn anode was also examined in an effort to understand the 2

high reversibility of the Zn/MnO2 cell chemistry. To a certain

degree, the reaction of MnO2 + H+ + e− ↔MnOOH in the present
Zn/MnO2 battery is similar to that in a MnO2 cathode in a primary
alkaline MnO2 battery31 . However, the critical difference lies in the
reaction at the Zn anode side. Figure 5 shows a comparison of
the stability and reversibility of a Zn/Zn symmetric cell in alkaline
and mild aqueous electrolytes. In the alkaline electrolyte, there is
a sudden increase in polarization after 12 h for only six cycles of
Zn stripping and plating. We ascribe this to the formation of an
insulating ZnO powder layer to a critical thickness, as shown by
the XRD pattern in Supplementary Fig. 7, and a loose and powder-
like of Zn plate surface after cycling in the alkaline electrolyte
(inset in Fig. 5a), which results from the irreversible reaction of
Zn + 2OH− →Zn(OH)2 + 2e− →ZnO + H2 O. In contrast, in
a mild 2 M ZnSO4 with 0.1 M MnSO4 aqueous electrolyte, the
Zn/Zn symmetric cell shows the excellent kinetics and stability
of Zn stripping/plating. After more than 120 cycles, the Zn plate
still exhibits a smooth, dense surface (inset of Fig. 5a). Figure 5b,c
shows a comparison of SEM images of Zn electrodes before and
after cycling. It can be seen that the Zn electrode exhibits a dense,
dendrite-free surface morphology after 120 cycles (Fig. 5b,c). A
similar surface morphology for the Zn anode was also observed
in a Zn/MnO2 full cell (Supplementary Fig. 9). This would be
very important for the long-term cycling stability of Zn/MnO2
batteries. The energy-dispersive X-ray (EDX) spectrum indicates
that the Zn deposition layer surface consists mainly of Zn metal,
resulting from the highly reversible plating/stripping of Zn metal in
mild electrolyte.
1
6
ZnSO4 [Zn(OH2 )]3 · xH2 O
Anode: 12 Zn ↔ 12 Zn2+ + e−
Overall: MnO2 + 12 Zn + x6 H2 O + 16 ZnSO4 ↔
MnOOH + 16 ZnSO4 [Zn(OH2 )]3 · xH2 O
Based on the total mass of cathode, anode and electrolyte
involved in the above reactions, these reactions provide an energy
density of ∼170 Wh kg−1 (at C/3). The available energy density
of the Zn/MnO2 battery is about five times higher than existing
commercial lead-acid batteries40 .
The combination of a highly reversible Zn anode and a MnO2
nanofibre cathode in a mild aqueous electrolyte (that is, 2 M ZnSO4
with 0.1 M MnSO4 in this research) presents a potentially high-
capacity aqueous battery chemistry with high reversibility and
high cycling stability, that is both environmentally benign and
safe. For practical applications, the electrochemical reactions and
stability need to be carefully evaluated. In particular, conversion
reactions involving both electrode materials and electrolytes are
more complex than intercalation chemistry. The reactions between
the cathode, anodes and electrolytes need to be carefully controlled
and optimized. Although this could be a significant challenge, a
good understanding and clarification of the fundamental reactions
in the Zn/MnO2 system is an important step towards a more
practical system in the future.
Conclusion
We studied the reversibility of aqueous Zn/MnO2 battery chemistry.
The MnO2 nanofibre cathode is highly reversible and stable

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ARTICLES
in a mild ZnSO4 aqueous electrolyte with a MnSO4 additive,
which suppresses Mn2+ dissolution into the electrolyte. This
Zn/MnO2 cell also exhibits an excellent rate capability and a
high-capacity retention of 92% after 5,000 cycles. The structural
and morphological evolution of α-MnO2 electrodes have been
comprehensively investigated by TEM and STEM–EDS mapping,
which explains the electrochemical behaviour and reveals an
alternative conversion reaction mechanism between MnOOH and
MnO2 other than Zn2+ ion intercalation into MnO2 . The high
reversibility of the Zn anode was also demonstrated in a mild ZnSO4
aqueous electrolyte. The combination of the reversible Zn anode and
the MnO2 cathode could lead to a promising battery chemistry that
is potentially highly reversible, highly stable and safe.
Methods
Material synthesis. In a typical synthesis of α-MnO2 , 0.003 M MnSO4 · H2 O and
2 ml 0.5 M H2 SO4 were added to 90 ml deionized water and magnetically stirred
until a clear solution was obtained. Then, 20 ml 0.1 M KMnO4 aqueous solution
was slowly added into the above solution. The mixture was stirred at room
temperature for 2 h. The solution was then transferred to a Teflon-lined autoclave
and heated at 120 ◦ C for 12 h. After cooling, the obtained material was collected
by centrifugation, washed three times with water, and dried using a vacuum oven
at room temperature.
Characterizations. X-ray diffraction (XRD) measurements were performed using
a Rigaku Miniflex II diffractometer with Cu Kα radiation (λ = 1.5406 Å). An FEI
Titan 80–300 microscope equipped with an objective lens corrector at 300 kV was
employed for the TEM images. Scanning/TEM and EDS mapping were
performed on a JEOL ARM200CF microscope at 200 kV, which is equipped with
a probe corrector and high-efficiency silicon drift EDS detector with a 100 mm2
X-ray sensor. 1 H Nuclear magnetic resonance (NMR) analyses were conducted
using a 1.6 mm HX probe using single-pulse excitation on a 600 MHz NMR
spectrometer (Agilent) under magic angle spinning at 35 kHz.
Electrochemical measurements. Using an electrochemical process, α-MnO2
electrodes were prepared by mixing α-MnO2 powder, carbon black and poly
vinylidene fluoride at a weight ratio of 7:2:1 in N -methyl pyrrolidone solvent,
then coating the slurry onto carbon sheets. The α-MnO2 mass loading is
1–5 mg cm−2 (Supplementary Fig. 8). Zn/MnO2 batteries were assembled using
an α-MnO2 electrode as the cathode, glass fibre as the separator and Zn foil as
the anode in CR2032 coin cells. The electrolyte used was 2 M ZnSO4
with/without 0.1 M MnSO4 as an additive in H2 O. The conventional alkaline
MnO2 batteries were assembled using a similar process, except for the use of
40 wt% KOH aqueous electrolyte. A symmetrical Zn/Zn cell was assembled using
Zn foil as both working and counter electrodes, using 2 M ZnSO4 with 0.1 M
MnSO4 as the electrolyte. 0.1 M ZnTf2 was dissolved into dimethyl sulfoxide
(DMSO) as an organic Zn electrolyte. For the water-addition organic electrolyte,
5 M H2 O was added into the above electrolyte. The charge/discharge was carried
out on a LANHER battery tester (Wuhan).
Received 28 October 2015; accepted 4 March 2016;
published 18 April 2016
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Acknowledgements
This work is supported by the US Department of Energy (DOE), Office of Basic Energy
Sciences, Division of Materials Sciences and Engineering, under Award
KC020105-FWP12152. The TEM, NMR and XRD work were performed using EMSL, a
National Scientific User Facility sponsored by the Department of Energy’s Office of
Biological and Environmental Research and located at PNNL. PNNL is a Multi-Program
National Laboratory operated for DOE by Battelle. The work at UW was supported by
Inamori Foundation.
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ARTICLES
Author contributions
Y.S. and J.L. proposed the research. H.P., Y.S. and J.L. designed the experiments. H.P. and
Y.S. performed the material process, characterization, electrochemical measurements and
analysed the data. Y.C. synthesized the material. P.Y., Y.C. and C.W. conducted the TEM
and STEM mapping. K.S.H. and K.T.M. performed NMR characterization. H.P.,
Y.S. and J.L. co-wrote the paper. All authors discussed the results and commented on
the manuscript.
Additional information
Supplementary information is available online. Reprints and permissions information is
available online at www.nature.com/reprints. Correspondence and requests for materials
should be addressed to Y.S. or J.L.
Competing interests
The authors declare no competing financial interests.
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