Electrochemistry Communications 60 (2015) 190–194

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Electrochemistry Communications

journal homepage: www.elsevier.com/locate/elecom

Charge storage mechanism of MnO2 cathodes in Zn/MnO2 batteries using

ionic liquid-based gel polymer electrolytes
Juan P. Tafur a, José Abad a, Elisa Román b, Antonio J. Fernández Romero a,⁎
a
Grupo de Materiales Avanzados para la Producción y Almacenamiento de Energía, Universidad Politécnica de Cartagena, Aulario II, Campus de Alfonso XIII, Cartagena 30203, Spain
b
Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Científicas (CSIC), C/Sor Juana Inés de la Cruz 3, Madrid 28049, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Cathode reactions in Zn/MnO2 batteries using aqueous electrolytes have been usually interpreted by the reduction of
Received 20 July 2015 Mn4+ to Mn3+ while protons and/or cations penetrate inside the cathode. However, until now, the MnO2 storage
Received in revised form 11 September 2015 charge mechanism using a non-aqueous gel polymer electrolyte (GPE) has not been investigated. In this work,
Accepted 12 September 2015
ionic liquid-based GPEs including BMIM Tf and ZnTf2 have been employed in Zn/MnO2 batteries. Different states
Available online 25 September 2015
of charge of MnO2 cathodes used in Zn/IL-GPE/MnO2 batteries have been analyzed by XPS and EDX techniques.
Keywords:
XPS analysis showed that Mn4+ is reduced during the discharge process at the same time as Zn2+ cations are incor-
Ionic liquid-based gel polymer electrolytes porated into the cathode. Besides, Zn2+ cations insertion is accompanied by triflate anions.
XPS © 2015 Elsevier B.V. All rights reserved.
MnO2 cathode
Zinc batteries

1. Introduction Currently, several research groups focus their investigation on GPEs

Zinc-based batteries have been extensively utilized due to their sever-
al advantages [1]. In addition, MnO2 is the most widely used cathode,
which can produce large discharge capacities, higher than 200 mAh g−1
with a practical potential of 1.3 V [2–4]. Until now, charge storage mech-
anism of MnO2 has been only investigated in aqueous electrolytes, and
two mechanisms have been proposed to explain it [5–7]. The first one
implies the intercalation of protons (H+) or metal cations (M+), such as
Na+ or Li+ during the reduction process:
MnO2 þ Hþ þ e– ↔MnOOH
MnO2 þ Mþ þ e– ↔MnOOM
The second mechanism involves the surface adsorption of cations on
MnO2:


ðMnO2 Þsurface þ Mþ þ e– ↔ MnO2 – Mþ surface
Intercalation of divalent cations, such as Mg2+ and Zn2+, into MnO2
have been recently reported, opening the development of an emerging
energy storage system: Zn2 + or Mg2 + ion batteries as most viable
candidates for replacing Li-ion batteries [2–4,8,9]. In this sense, Oh
et al. have published a series of papers describing the intercalation of
Zn2+ cations into different MnO2 structures [4,8,9].
⁎ Corresponding author. Tel.: +34 968 325580; fax: +34 968 325931.
E-mail address: antonioj.fernandez@upct.es (A.J. Fernández Romero).
to be applied in different storage systems, including lithium, zinc, or
magnesium batteries [10–13]. A lot of these batteries use MnO2 cath-
odes, although until now the charge store mechanism of MnO2 in
GPE-based batteries has not been studied in detail.
In this communication, we present the first results obtained in the
investigation of the MnO2 charge storage mechanism in a Zn/MnO2 bat-
tery using a non-liquid electrolyte: a new GPE based on BMIM TF IL and
ZnTf2 salt.
2. Experimental
ð1Þ
1-Buthyl-3-methylimidazolium trifluoromethanesulfonate, 99%
ð2Þ (BMIM TF) was purchased from IOLITEC. The co-polymer poly(vinylidene
fluoride-co-hexafluoropropylene) (PVdF-HFP), tetrahydrofuran (THF),
n-methyl-2-pyrrolidone (NMP), and zinc trifluoromethanesulfonate
(ZnTf2) were obtained from Sigma–Aldrich. XPS spectra were recorded
using a hemispherical analyzer. Non-monochromatized Mg Kα
ð3Þ (1253.6 eV) X-rays were used. The data are analyzed after removal
the Mg Kα satellite lines, subtraction of a Shirley type background,
and charge referenced to adventitious C1s peak at 284.8 eV.
Energy dispersive X-rays (EDX) analysis was carried out with a
scanning electron microscope S-3500 N.
Galvanostatic charge/discharges were carried out using a Biologic
VSP Modular 5 channels potensiostat/galvanostat. Cathode materials
were prepared as it has been reported previously [13].
GPEs were synthesized using a solution cast method: PVdF-HFP, IL,
and ZnTf2 were dissolved in NMP. To know more about the synthesis
and characterization of this kind of GPEs, see ref. [13].

http://dx.doi.org/10.1016/j.elecom.2015.09.011
1388-2481/© 2015 Elsevier B.V. All rights reserved.
 J.P. Tafur et al. / Electrochemistry Communications 60 (2015) 190–194
Fig. 1. First discharge and subsequent recharge curves of a Zn/IL-GPE/MnO2 battery at
6.25 mA g−1. The cut off voltage was 0.4 V for the discharge process.
Charge/discharge measurements of Zn/IL-GPE/MnO2 batteries have
been carried out at the current range between 6.25 and 2000 mA g−1.
Specific capacities varied with the current density increasing from
Fig. 2. Three regions of XPS spectra of as-prepared, discharged, and recharged MnO2 electrodes: A) Mn2p3/2, B) Zn2p, and C) C1s.
191
125 mAh g−1 for 6.25 mA g−1 to 78 mAh g−1 for 2000 mA g−1. These
values are comparable to those obtained previously for different Zn/
MnO2 batteries [14,15].
3. Results and discussion
In this paper, the charge/discharge curves of the Zn/IL-GPE/MnO2
battery were carried out at 6.25 mA g−1, resulting a discharge capacity
higher than 120 mAh g−1 (Fig. 1). Specific capacity was calculated in
base on the cathode active material, that is, the initial weight of the
active MnO2 in the cathode.
With the aim to analyze the charge store mechanism of the MnO2
cathode, an XPS study was carried out. Fig. 2a shows the Mn 2p spectra
of the cathode material at various states of charge: as-prepared,
discharged, and recharged. The observed binding energy (B.E.) of Mn
2p3/2 (642.4 eV) peak for as-prepared electrode is consistent with the
presence of Mn4+, indicating that MnO2 is present in the initial material.
After discharge process, this peak is shifted to lower B.E. (642.1 eV),
confirming that Mn4 + is reduced. During recharging the majority of
the reduced species were reoxidized to Mn4 +, as it is confirmed by
the shift of the Mn 2p3/2 peak to the initial BE value (642.4 eV) of the
as-prepared electrode [7,16,17].
Attention must be paid in the shoulder observed at 647.4 eV
(marked with an arrow) for the discharged cathode, which has been
reported as a satellite peak related with the formation of Mn2+ species
192 J.P. Tafur et al. / Electrochemistry Communications 60 (2015) 190–194
[16–18]. This peak is not observed when MnO2 or Mn2O3 is formed [18].
Note that this shoulder is also lightly observed for the recharged cathode,
indicating that part of the Mn2+ species could be not oxidized into the
Mn4+. Unfortunately, Mn 3s region cannot be used to confirm the state
of oxidation of Mn because Zn 3p peaks appear in this region overlapping
the Mn 3s peaks.
This fact points to the inclusion of Zn2+ into the MnO2 cathode
during the discharge process, which is confirmed in Fig. 2b where the
Zn 2p region is displayed. For discharged cathode, intense Zn peaks
appear shifted to higher B.E. with respect to the non-used Zn plate.
Hence, it can be deduced that Zn2 + cations are intercalated into the
cathode during the discharge process. However, these peaks are also
observed for the recharged cathode, confirming that not all of the
Zn2+ cations were extracted from the cathode during charging.
Here, we have to remember the two processes proposed to explain
the charge storage mechanism of MnO2 in aqueous electrolytes (reaction
1–3). However, the batteries used in this work include a non-aqueous
ionic liquid-based GPE, which has not free protons available to be interca-
lated into the MnO2. Thus, only Zn2+ cations may ingress into the cathode
during the reduction process, as it is observed in the XPS spectra. Further-
more, intercalation of Zn2+ cations in MnO2 electrodes has been recently
reported by other groups [4,8,9].
Moreover, XPS is a surface technique and only can probe the top
1–3 nm of the surface [19]. Thus, it could be thought that the Zn2+
cations are adsorbed on the cathode surface during the discharge
process, as it indicates the reaction (3), proposed for MnO2 batteries
using aqueous electrolytes. Effectively, SEM micrograph obtained for
the discharged and recharged cathode materials showed very different
appearances. The image of discharged cathode presents several white
spots, probably due to ZnTf2 salt deposited on the cathode material.
Furthermore, Tf− anions are detected in the XPS measurements, as it
is observed in C1s region showed in Fig. 2c. A peak at ~ 293.5 eV due
to –CF3 triflate group appeared in discharged and recharged cathodes,
Fig. 3. SEM images and EDX spectra of discharged MnO2 electrodes at three different deeps (A, B, and C). SEM image and EDX spectrum of recharged MnO2 electrode (D). The crosses
indicate where the EDX was realized. In these images, the MnO2 side in contact with the IL-GPE during the charge and discharge processes is at the top.
indicating that triflate anions penetrate during the discharge process
and they are not totally expulsed during the recharge process. Besides,
a peak is observed at ~ 169 eV (not shown), which has been assigned
to S of triflate [20].
With the aim to know how much depth Zn2+ cations penetrate in
the cathode, we have carried out an additional EDX analysis. To perform
these measurements, we have broken the cathodes by the middle and
the interior of the cathode was analyzed at three different deeps. Fig. 3
shows SEM micrographs and the EDX spectra measured in the points
marked with green crosses. EDX spectra confirm the presence of Zn
along the whole discharged cathode depth. Therefore, we can confirm
that Zn2+ cations are intercalated in the whole cathode. However, Zn
peaks are also observed in the recharged electrode, indicating that Zn
cations are not totally extracted from the cathode during the recharge
process. Note that S peak was also observed in discharged and charged
electrodes, confirming that triflate anions penetrate into the cathode
material during the discharge process, but they are not completely
expulsed from it during recharging. Probably some Zn2+ cations could
be stabilized inside the electrode by the triflate anions.
With the aim to explain the reduction of Mn4+ to Mn2+ during the
discharge process, we can consider the works of Kumar et al. [21,22],
where a two-step reduction of MnO2 was proposed for a Mg/GPE/
MnO 2 battery, because two plateaus were observed during the
discharge:
h i
2MnO2 þ Mg2þ þ 2e− → 2MnO2 − Mg2þ ð4Þ
h i h i
2MnO2 − Mg2þ þ Mg2þ þ 2e− → 2MnO2 2− 2Mg2þ ð5Þ
Thus, Mn4+ is reduced to Mn3 + in the first reaction and Mn3 + is
reduced to Mn2+ in the second one. In these processes, intercalation
 J.P. Tafur et al. / Electrochemistry Communications 60 (2015) 190–194
Fig. 4. SEM image of Zn-contact IL-GPE face after the discharge process and EDX spectra of Zn-contact IL-GPE face for discharged (red) and recharged (blue) MnO2 cathodes.
of Mg2+ cations from the GPE was also proposed, although direct detec-
tion of cations inside the cathode was not carried out.
Mn4+/Mn2+ reduction has been also reported by other authors [4,
17,23]. Devaraj et al. [17] have studied the galvanostatic charge/
discharge of Li/Li2MnSiO4 batteries using a non-aqueous liquid electro-
lyte (LiPF6 in EC and DEC). They proposed that Li+ cations are inserted
into the cathode material during discharging while Mn4+ was reduced
to Mn2+. Inversely, during charging, Li+ are extracted from the cathode
and the Mn2+ is oxidized to Mn4+. Although Mn3+ species seem to be
formed during the discharge, they observed only a flat plateau.
On the other hand, formation of Mn2+ has been frequently reported
as a product of the chemical disproportionation of Mn3+ [4,23]:
2Mn3þ ðsÞ→Mn2þ ðaqÞ þ Mn4þ ðsÞ
However, we consider unlikely that the disproportionation reaction
is produced when a non-aqueous GPE is used.
Returning to our battery, a preliminary voltammetric study of a
MnO2 electrode carried out in NMP-BMIM Tf-ZnTf2 solution produced
two reduction peaks, which can be assigned to the redox pairs Mn4+/
Mn3 + and Mn3 +/Mn2 +. This result points to a two-step process,
although only a plateau was observed during the discharge. Considering
the above factors and our results, a next general mechanism can be
proposed to the discharge process of Zn/IL-GPE/MnO2 batteries:
h i
2MnO2 þ Zn2þ þ 2e− → 2MnO2 −Zn2þ
193
h i h i
2MnO2− Zn2þ þ Zn2þ þ 2e− → 2MnO2 2− 2Zn2þ ð8Þ
Furthermore, it is known that the solubility of Mn2 + in water is
typically high [4], but we wonder whether Mn2 + species would be
soluble in the GPE. With this aim, we have registered EDX spectra of
the zinc-contact face of the GPE used in the batteries (Fig. 4). As can
be seen, a Mn peak is observed to the GPE used in the discharged
battery, but it is not observed in the GPE of the recharged one. Hence,
we can confirm that Mn2+ ions were accumulated in the GPE during
the discharge, but during the recharge process these ions returned to
the cathode. Moreover, Mn peak is not observed when EDX was
ð6Þ performed to the zinc electrode used during charging, indicating that
Mn2+ is not reduced to Mn0 in the anode during the recharge process.
4. Conclusions
In this work, we have found evidence of the MnO2 storage charge
mechanism using a non-aqueous gel polymer electrolyte (GPE), which
can be relevant to the development of emerging Zn2 + ion batteries.
We have demonstrated the reduction of Mn4+ to Mn2+ species, at the
same time as Zn2+ cations intercalate the cathode material during the
discharge process. Moreover, triflate anions penetrate into the cathode
electrode together Zn2+, while the Mn2+ species are expulsed towards
the GPE. During the recharge process, Mn2+ species return to the positive
ð7Þ
electrode and they are oxidized mainly to Mn4+. However, in this process,
194 J.P. Tafur et al. / Electrochemistry Communications 60 (2015) 190–194
Zn2+ cations are not totally expulsed, remaining inside the electrode,
probably stabilized by the triflate anions which are not expulsed either.
Acknowledgements
The authors thank the financial support from the Spanish Ministerio
de Economía y Competitividad (Ref. ENE2013-48816-C5-3-R).
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