Electrochimica Acta 220 (2016) 635642

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

High alkaline tolerant electrolyte membrane with improved

conductivity and mechanical strength via lithium chloride/
dimethylacetamide dissolved microcrystalline cellulose for Zn-Air
batteries
Yuansong Zhanga, Cong Lib,**, Xiaoxia Caia,*, Jinshui Yaoa, Mei Lia, Xian Zhanga, Qinze Liua
a
Key Laboratory of Processing and Testing Technology of Glass Functional Ceramics of Shandong Province, School of Materials Science and Engineering, Qilu
University of Technology, Jinan, 250353, PR China
b
Biomaterials and Technology Lab, Department of Grain Science and Industry, Kansas State University, 1980 Kimball Ave., BIVAP Bldg, Manhattan, Kansas
66506 USA

A R T I C L E I N F O A B S T R A C T

Article history:
Received 24 June 2016 LiCl/DMAc (dimethylacetamide) solution dissolved microcrystalline cellulose (LD-MCC) showed
Received in revised form 12 October 2016 potential benets to the alkaline solid polymer electrolyte (ASPE). High alkali tolerance (up to 70 wt%
Accepted 15 October 2016 KOH loading), remarkable improvements in ionic conductivity (from 0.018 S cm 1 to 0.153 S cm 1) and
Available online 18 October 2016 mechanical properties (3-fold increase in tensile strength from 0.28 MPa to 0.76 MPa) were achieved just
via an incorporation of 5 wt% of LD-MCC into the ASPE matrix. Wide-angle X-ray diffraction indicated that
Keywords: LD-MCC entrapped KOH and hindered its aggregation. X-ray Energy Dispersive Spectrometer revealed
Alkaline polymer electrolyte that K+ was preferentially located on the LD-MCC surfaces rather than the polymeric matrix. Scanning
MCC
Electron Microscopy of freeze-dry sample demonstrated a submicro-porous morphology with reduced
PVA
average pore size (175 nm) after the incorporation of LD-MCC in ASPE matrix. The incorporated LD-MCC
acted as KOH stabilizer, hydrophilicity agent and OH transport media. Distinct micro-structures before
and after the incorporation of LD-MCC were investigated to reveal the special role of LD-MCC in the
performance improvement of ASPE membrane.
2016 Elsevier Ltd. All rights reserved.

1. Introduction
In the past decades, extensive research have endeavored in
developing alkaline solid polymer electrolyte (ASPE) instead of the
aqueous alkaline solutions because of its nontoxic, low-leakage,
abundance in the basic components, and good ionic conductivity [1
5]. Since Fenton et al.s report about the complexes of alkali metal
ions with poly(ethylene oxide) (PEO) in 1973, PEO-based solid lms
have been considered for ASPE membrane application [6,7].
However, PEO tends to crystallize, especially at high salt concentra-
tion, which results in a dramatic decrease of conductivity and limits
their application in electrochemical devices [8]. Compared to PEO,
another exible hydrophilic polyvinyl alcohol (PVA) with high
hydrophilicity capacity was also selected as solid electrolytes base
material. However, at higher KOH concentration, the PVAKOH
* Corresponding author.
** Co-corresponding author.
E-mail addresses: congli@ksu.edu (C. Li), cxx424@hotmail.com (X. Cai).
complex lms seemed to be not strong enough and showed low
conductivity about 10 4 S cm 1 at room temperature [9,10].
One of main methods for enhancing the ionic conductivity of
solid electrolytes is to increase the contents of alkali and H2O. The
reason is that the ionic conductivity of the solid alkali polymer
electrolyte is very dependent on the content of alkali and H2O [11].
Some researches added liquid alkaline into anion-exchange basic
membranes [9,11]. Even though, the ionic conductivity at room
temperature was as low as 10 3 S cm 1. Moreover, the increase of
alkali content can impair the mechanical properties because of the
chain-broken caused by the excess alkali [9,12]. In order to achieve
a good balance between enhanced ionic conductivity and desired
mechanical strength, most studies have focused on utilizing cross-
linked structure by immersing ASPE membranes in alkali solution
with various concentrations [3,1316]. Although the ionic conduc-
tivity has been improved, there is a latent instability in the
mechanical and electrochemical properties because most alkali
solutions were preferentially located on the surface of membrane
with the increase of time. This may resulted in a brittle lm with
poor performance [17].

http://dx.doi.org/10.1016/j.electacta.2016.10.103
0013-4686/ 2016 Elsevier Ltd. All rights reserved.
 636 Y. Zhang et al. / Electrochimica Acta 220 (2016) 635642
[(Schem_1)TD$FIG]
Improved ionic conductivity without impairing mechanical
strength is signicant for the design of ASPE with high alkali
content. Cellulose, the intriguing natural materials possess high
density of hydroxyl groups which afford a higher level of
hydrophilicity. Moreover, the stable existence of crystal cellulose
II in aqueous NaOH solution [18] indicated its high alkali tolerance.
Inspired by these properties, we introduced microcrystalline
cellulose (MCC) to the ASPE matrix through dissolving it in the
solution of N,N- Dimethylacetamide/Lithium Chloride (DMAc/LiCl)
[19,20]. The effective dissolution of MCC in DMAc/LiCl system Scheme 1. Schematic diagram showing the interaction of LD-MCC and KOH for
guaranteed the destruction of amorphous MCC phases and enhancing the alkali stability of PVA/PEO system.
achieved the homogeneous dispersion of crystal phases in ASPE
matrix. We assumed this structure would favor the entrapment of 20 mm (Sigma-Aldrich Corp.), KOH (AR, the Reagent Factory of
KOH on the cellulose surface. Moreover, the hydrophlicity of MCC Tianjin, China), Lithium chloride (AR, Sigma-Aldrich Corp.), and N-
would entrap more water in the polymeric matrix and the high N-Dimethylacetamide (DMAc, Chemical Reagent Factory of Tianjin,
modulus of MCC would be favorable for the improvement of China) were used as received.
mechanical properties of ASPE. By changing the added content of
DAMc/LiCl pretreated MCC, the hydroxyl anion transportation in 2.2. Preparation of composite alkaline membrane
ASPE matrix would be regulated, and a PEO/PVA based solid
polymer electrolytes with high alkali tolerance, signicantly Firstly, 2.4 g PVA and 0.6 g PEO were dissolved in 20 ml
improved conductivity and mechanical strength would be deionized water with agitation at rotation of about 600 rpm at
expected. 80  C to obtain a homogeneous PVA/PEO aqueous solution.
Secondly, MCC was dissolved in LiCl/DMAc solvent system. Various
2. Experimental Section contents of MCC (from 1 wt% to 5 wt%) were added to 0.35 g LiCl/
5 ml DMAc with magnetic agitation for 5 h at 80  C to obtain a
2.1. Materials homogeneous solution and the LiCl/DMAc treated MCC was named
as LD-MCC. Thirdly, the LD-MCC solution and PVA/PEO aqueous
PVA (Ma = 80,000, AR, Chemical Reagent Factory of Tianjin, solution were mixed together and stirred continuously to obtain a
China), PEO (Ma = 100,000, AR, Chemical Reagent Factory of Tianjin, homogenous solution. Finally, aqueous solution with varied KOH
China), Microcrystalline Cellulose (MCC) with the diameter of content was dropwise added into the PVA/PEO/LD-MCC solution at
[(Fig._1)TD$IG]

Fig. 1. Pictures of PVA/PEO/LD-MCC/KOH alkaline polymer electrolyte membranes (A) PVA/PEO/KOH (7 g); (B) 7 g PVA/PEO/LD-MCC5/KOH (7 g); (C) PVA/PEO/KOH (8 g); (D)
PVA/PEO/LD-MCC5/KOH (8 g).
 Y. Zhang et al. / Electrochimica Acta 220 (2016) 635642
[(Fig._2)TD$IG]
Fig. 2. The SEM microphotographs of cross-section for alkaline polymer electrolyte membranes of (A) PVA/PEO/KOH(7 g); (B) PVA/PEO/LD-MCC5/KOH(7 g) (C) Pore size
distribution of the submicro-porous structure for (A) and (B); (D) EDX for spot A (MCC-rich zone) and spot B (polymeric zone) of PVA/PEO/LD-MCC5/KOH(7 g) membrane.
continuous stirring until the solution took on a homogeneous
appearance. The resulting homogeneous polymer solution was
then poured onto a PTFE plate to form a lm. The excess water
solvent was further evaporated slowly in a vacuum oven at 40  C
and 50% relative humidity (RH) condition. The thickness of the
polymer membrane was measured by a vernier caliper in the range
of 0.60.8 mm. By changing the content of LD-MCC of 0, 1, 5, and
10 wt% and changing the added weight of KOH of 3 g, 4 g, 5 g, 6 g,
7 g, and 8 g, a series of PVA/PEO/LD-MCC(x)/KOH(y) polymer
electrolytes membranes were prepared, where the x indicates the
content of LD-MCC in PVA and PEO matrix, and the y indicates the
added weight of KOH in the system.
2.3. ZnAir battery design and assembly
Preparation of air electrode: The carbon slurry for the active
layer of the air electrode was prepared by mixing of acetylene
black, KMnO4, Carbon black (Vulcan XC-72R), Na2SO4 and
polyvinylidene uoride (PVDF) with weight ratios of 1: 4: 1: 4:
1, and then dissolved by ethyl alcohol. The resultant mixture was
stirred continuously at room temperature to achieve slurry. Finally,
the obtained slurry was coated on nickel foam manually and
pressed at 80 kg/cm2 for 0.5 h. The thickness of the obtained air
electrode was about 0.5 mm.
Preparation of zinc electrode: The zinc electrode was prepared
by mixing of zinc powder and PVDF with the weight ratios of 10:1,
and the resulted mixture was blended with n-methyl-pyrrolidone
637
to obtain homogeneous sticky substance. Then, the sticky
substance was coated on the other nickel foam under a pressure
of 80 kg/cm2 for 0.5 h [21].
Zn and air electrodes were placed in the oven at 100  C for the
purpose to evaporate the left solvent.
Assembling of alkaline polymer electrolyte ZnAir battery:
Solid-state Znair cells with the PVA/PEO/LD-MCC/KOH alkaline
polymer electrolyte consist of zinc electrode, polymer electrolyte
and air electrode. The above three parts were arranged in turn to
form sandwich structure and packaged in battery shell with a
micropore for the oxygen circulation.
2.4. Morphological and structure characterization
The morphology of PVA/PEO/LD-MCC/KOH alkaline polymer
electrolyte membrane was investigated by scanning electron
microscopy (SEM, JSM-7500F, JEOL Ltd., Japan). The specimens
were freeze-dried, frozen under liquid nitrogen, then fractured,
mounted, coated with gold, and observed.
Energy-dispersive X-ray spectroscopy (EDX) analysis of the
polymer electrolyte membranes were performed using a scanning
electron microscopy spectrometer (Octane Pro SDD, EDAX).
Acceleration voltage is 20 kV, integration time is 60 s, estimated
ROI volume due to the excitation volume of the electron beam is
about 0.5 mm2, and the beam-sample distance is 15.7 mm.
The pore size distribution was determined through the
statistics of normal distribution of pore diameters. Here, software
638 Y. Zhang et al. / Electrochimica Acta 220 (2016) 635642
Nano Measurer 1.2 was used to measure the pore size and obtain
the raw data. Size distribution diagram was then obtained by
importing raw data into the software Origin 8.0 to draw the normal
distribution.
Wide angle X-ray diffraction (WAXD) measurements were
carried out on a XRD diffractometer (XRD-6100, SHIMADZU Ltd.
Japan). The patterns with Cu Ka radiation at 40 kV and 30 mA were
recorded in the region of 2u from 10 to 70 . Conditioned
membranes were mounted on a poly (methyl methacrylate)
(PMMA) hollow support and sealed with a thin aluminum foil in
order to preserve moisture conditions of 50% RH during the
experiment.
Thermogravimetry analysis (TGA) of the polymer electrolyte
membranes were performed via a TGA1 STARe system apparatus
(TG7, METTLER TOLEDO, Switzerland). Samples of about 10 mg
were loaded into an alumina pan, and then heated from 45 to
800  C at a rate of 10  C min 1 under nitrogen atmosphere.
2.5. Properties Characterization
The ionic conductivity of the PVA/PEO/LD-MCC/KOH alkaline
polymer electrolyte was measured by an AC impedance method via
an electrochemical impedance analyzer (CHI660E, Shanghai
Chenhua Instruments Co., China) at room temperature, where
the AC frequency was scanned from 105 to 10 2 Hz with an
amplitude of 5 mV. The samples with diameter of 1 cm were
sandwiched between two stainless steels with the surface area of
0.785 cm2 (SS|SPE|SS). The bulk resistance Rb was determined from
the cross point of the Ninquist curve at the real axis. The calculation
formula of ionic conductivity is s = L/(Rb  A), where L, Rb and A are
on behalf of the thickness (cm), bulk resistance (ohm) and area
(cm2) of the sample, respectively.
The electrochemical stability window was determined by a
cyclic voltammetry curve which was tested by CHI660E Electro-
chemical Workstation. The samples with the radius of 0.5 cm were
placed between two stainless steels (SS|SPE|SS). PVA/PEO/LD-
MCC/KOH alkaline polymer electrolyte membranes were cycled in
the voltage region of 1.5 V to 1.5 V with a scan rate of 10 mV s 1 at
25  C.
The charge-discharge performance of the battery was tested
using LAND auto-cycler (CT2001A, Wuhan Blue Electrical Co.,
China). The extent of electric current for charging and discharging
of Zn-air cells was determined according to a calculation method
I = (m-m0)*1 mA/g, here m and m0 were the weight (g) of zinc
electrode and nickel foam, respectively.
The mechanical properties of PVA/PEO/LD-MCC/KOH alkaline
polymer electrolyte membranes were evaluated by a mechanical
testing machine (WDL-005, JinanXinshijin Experimental Instru-
ment Co., China), with a crosshead speed of 20 mm/min. The
specimens with typical size of 30mm  11 mm (length  width)
were used and coated with silicone wax to avoid water evaporation
during the experiment.
3. Results and discussion
3.1. The effect of LD-MCC on the alkali stability
In general, the anion conductivity of alkaline polymer electro-
lyte membrane is greatly dependent on the content of KOH [9,11].
However, high KOH content has the trend to apparent aggregation
of KOH, resulting in the heterogeneous and non-stoichiometric
composite electrolyte as well as the poor mechanical property of
ASPE [9,11,22]. Fig. 1 shows the effect of LD-MCC on the
morphology of PVA/PEO/KOH alkaline polymer electrolyte mem-
branes. When 7 g KOH was added to PVA/PEO, lots of gel spots were
formed, as shown in Fig. 1A. With the increase of KOH content, the
membrane turned into a white clot (Fig. 1C). This implied that the
aggregation of excess KOH in ASPE impaired the formation of the
membrane. While after an incorporation of 5 wt% LD-MCC, integral
lms with relatively smooth surfaces formed for both PVA/PEO/
KOH (7 g) and PVA/PEO/KOH (8 g) (Fig. 1B and D). These interesting
results indicated that LD-MCC probably had remarkable enhancing
effect on the alkali tolerance of ASPE. This can be derived from the
interaction between KOH and LD-MCC via hydrogen bonds, as
Scheme 1 shows, in which KOH could be entrapped on the MCC
surfaces. A relatively higher K+ ion content on the surface of LD-
MCC (e.g. spot A in Fig. 2B) compared to the polymeric matrix (e.g.
spot B in Fig. 2B) was identied by the EDX spectra (Fig. 2D). In
order to conrm the preferential accumulation of K+ on the
LD-MCC surface, we obtained more data by conducting EDX test at
different locations (see Fig.S1 and Fig.S2 in the supplementary
data). In addition, it was speculated that the incorporation of
LD-MCC destroyed the aggregation of KOH and a weakening of KOH
crystal peaks (2u from 27 to 35 , shown in Fig. 4B) with the
increase of LD-MCC content can be recognized.
3.2. Morphology and Structure Analyses
The surface morphologies of the membrane fracture after
freeze-dried were observed by SEM. As the micrographs shown in
Fig. 2A and B, the formed submicron-porous structure implies that
the pores were probably lled with water before the freeze-dried
process. Pore size distributions of PVA/PEO/KOH (7 g) and PVA/
PEO/LD-MCC5/KOH (7 g) membranes are summarized in Fig. 2C.
With the addition of 5 wt% LD-MCC, the averaged diameters of
pores decreased from around 225 nm to 175 nm (Fig. 2C).
Moreover, it was found a higher K+ content on the LD-MCC
surface (e.g. spot A in Fig. 2.B) than that on the polymeric matrix
(e.g. spot B in Fig. 2B) based on the EDX results (Fig. 2D) discussed
in section 3.1.This indicated that the K+ was preferentially located
on the LD-MCC surfaces rather than the polymeric matrix. We
believe that the reason was probably due to the high density of
hydroxyl groups on the LD-MCC surfaces, by which effective
hydrogen bonds between KOH and hydroxyl groups of LD-MCC
were generated (Scheme 1). The distinct morphology after the
incorporation of LD-MCC provided a possibility for signicantly
improving the alkaline membrane conductivity and mechanical
properties. Relative to PVA/PEO/KOH (7 g), the higher dense pore
distribution and reduced average pore size (175 nm) after the
incorporation of LD-MCC increased the interfacial area between
aqueous and solid phase as well as the water retention capacity.
TGA curves further conrmed the increased water retention
capacity of membrane after the incorporation of LD-MCC. As
shown in Fig. 3, the weight loss during 50  150  C was attributed
to the water evaporation and showed a maximum weight loss
percentage of about 50% for PVA/PEO/LD-MCC1/KOH/(7 g) and
PVA/PEO/LD-MCC5/KOH/(7 g), whereas without addition of LD-
MCC, the weight loss percentage of PVA/PEO/KOH/(7 g) was only
about 43%. Obviously, the high density hydroxyl group on the
surface of LD-MCC could entrap more amounts of water molecules
which are benet for the transport of hydroxide ions in aqueous
medium [11,23]. With the increase of LD-MCC content, the water
retention capacity decreased as the TGA curve of PVA/PEO/LD-
MCC10/KOH/(7 g) shown, which was probably due to the
aggregation of LD-MCC and a corresponding decreased conductiv-
ity was also found in Fig. 5. As Grotthuss mechanism proposed, the
majority of OH transport in ASPE was realized by means of
hydrogen bond formation and cleavage along chains of water
molecules as well as the surface site hopping along chains of
polyelectrolyte polymers [23]. Therefore, it can be deduced that
more portion of OH took part in the transport in LD-MCC
incorporated membrane, in which higher content of alkaline
 Y. Zhang et al. / Electrochimica Acta 220 (2016) 635642
[(Fig._3)TD$IG]
Fig. 3. TGA curves for PVA/PEO/KOH (7 g) alkaline polymer electrolyte membranes
with 0, 1, 5, 10 wt% LD-MCC, where the inserted curves show the TGA curve at the
temperature range of 45150  C.
aqueous components and solid-aqueous interfaces increased the
contact frequencies of OH and H2O or -O in PVA and PEO
backbones. Correspondingly, an improved ASPE conductivity can
be expected.
Fig. 4 shows the X-ray diffraction patterns of PVA/PEO/LD-MCC
alkaline polymer electrolytes. It is well known that PVA exhibits
the characteristic absorption of semi-crystalline peaks at 2u = 20
[9]. There was no obvious absorption peak of PEO because of its low
[(Fig._4)TD$IG]
639
percentage in samples. As shown in Fig. 4A, the peak intensity at 2u
of 20 from PVA was greatly reduced when KOH was introduced.
This could be due to the disruption of the PVA crystalline structure
by KOH. The resulting amorphous PVA can enhance the ionic
conductivity because of the exibility of local chain segmental
motion in the polymer matrix [9]. Another region should be
noticed is the broad small peaks ranging from 27 to 35 . The peaks
appeared in this range were attributed to the diffraction of KOH
crystal [24], demonstrating the KOH aggregates in ASPE polymeric
matrix. As Fig. 4B shown, with the increase of LD-MCC content,
these peaks disappeared gradually, indicating that the LD-MCC
disrupted the aggregation of KOH molecules and a more
homogeneous distribution of KOH in ASPE matrix was achieved.
The reason was probably due to the interaction of LD-MCC and KOH
through hydrogen bonds, by which the K+ was preferentially
located on the LD-MCC surfaces rather than the polymeric matrix,
consistent with the EDX result previously discussed. So, the
disruption of KOH aggregates could increase the amount of KOH
molecules taking part in the transport of hydroxide ions and
improve the conductivity efciency. The key morphology features
of the LD-MCC incorporated PVA/PEO/KOH membrane were
presented in Scheme 2 to illustrate the relationship between
ionic conductivity and the ASPE internal structure.
3.3. Property Evaluation
3.3.1. Electrochemical Properties
All the alkaline polymer electrolyte membranes were measured
by AC impedance at ambient temperature. The AC impedance
spectra for PVA/PEO/LD-MCC/KOH(7 g) alkaline polymer electro-

Fig. 4. WAXD scans for (A) PVA/PEO (weight ratio of 4:1), LD-MCC and PVA/PEO/LD-MCC/KOH (7 g) alkaline polymer electrolyte membranes with various content of LD-MCC
at the 2u range of 10 70 , and (B) KOH and PVA/PEO/LD-MCC/KOH (7 g) alkaline polymer electrolyte membranes with various content of LD-MCC at the 2u range of 27 35 ..

[(Fig._5)TD$IG]

Fig. 5. (A) The AC impedance spectra for the alkaline polymer electrolyte membranes of PVA/PEO/KOH(7 g) with (a) 0, (b) 1, (c) 5, and (d) 10 wt% LD-MCC, respectively. (B)
Ionic conductivity of polymer electrolytes membranes as a function of added KOH weight at 25  C with (a) 0, (b) 1, (c) 5, and (d) 10 wt% LD-MCC, respectively.
640 Y. Zhang et al. / Electrochimica Acta 220 (2016) 635642
[(Schem_2)TD$FIG]

Scheme 2. Schematic diagram showing the key structural features of PVA/PEO/KOH membranes without (A) and with LD-MCC (B). LD-MCC entrapped KOH and water
through the interactions of hydrogen bonds. In this way, compared to case (a), the incorporation of LD-MCC (case (B)) provided more opportunities for OH transfer via the
surface site hopping along the chains of polyelectrolyte polymers and the chains of water molecules.

lyte lms with various contents of LD-MCC were shown in Fig. 5A.
Properties of the composite polymer electrolyte, such as the bulk
resistance and Rb can be derived from the spectra. Typically, Rb
values for the PVA/PEO/LD-MCC/KOH(7 g) alkaline polymer
electrolyte membranes are of the order of 0.51.6 V, and are
dependent on the contents of LD-MCC. In terms of the calculation
formula s = L/(Rb  A), the Rb value was converted into ionic
conductivity, s. The ionic conductivity values of PVA/PEO/LD-MCC/
KOH polymer electrolytes with different contents of KOH and LD-
MCC were shown in Fig. 6B. It was observed that the conductivity
of the sample increased to the maximum rst when the KOH
weight was increased from 3 g to 7 g, and then decreased provided
the same LD-MCC loading. We also found that a 5 wt% LD-MCC
loading produced the highest ionic conductivity in the composite
polymer electrolytes membrane. The effect of the LD-MCC content
on the ionic conductivity may be explained by the increased water
and KOH retention capacity as well as the increased contact
frequencies of OH and H2O or -O in the PVA and PEO
backbones, as discussed in the previous section. The highest value
[(Fig._6)TD$IG]
of ionic conductivity at room temperature for the composite
alkaline polymer membrane electrolytes is 0.153 S cm 1.
For pragmatic application of alkaline polymer electrolytes in
batteries, not only high conductivity but also wide electrochemical
stability window should be required. The electrochemical stability
windows of PVA/PEO/LD-MCC/KOH (7 g) alkaline polymer electro-
lyte membranes with 0, 1, 5, and 10 wt% LD-MCC are determined by
cyclic voltammetry (CV) method, and the electrochemical stability
windows are dened as a region of potential where no consider-
able faradic current ows through the electrolyte [25]. The cyclic
voltammetry (CV) curve of SS | ASPE | SS cell is shown in Fig. 6. It
was speculated that the concentration and the diffusion coefcient
of OH in the ASPE membrane had signicant affect on the slope of
CV curve [26]. For the diffusion coefcient in our case, the different
LD-MCC loadings resulted in the different values. This was because
the incorporation of LD-MCC into the ASPE membrane changed the
interfacial area between aqueous and solid phase as well as the
water retention capacity. Consequently, different contact frequen-
cies of OH and H2O or -O in the PVA and PEO backbones can
[(Fig._7)TD$IG]

Fig. 6. The cyclic voltammetry curves of PVA/PEO/LD-MCC/KOH (7 g) alkaline

polymer electrolyte membranes with various content of LD-MCC at 25  C with the Fig. 7. The typical discharge curve for Zn-air battery with PVA/PEO/LD-MCC5/KOH
scan rate of 10 mV s 1. (7 g) alkaline polymer electrolyte membrane.
 Y. Zhang et al. / Electrochimica Acta 220 (2016) 635642
[(Fig._8)TD$IG]
Fig. 8. (A) The stress-strain curves and (B) the tensile strength, Youngs modulus and elongation at break for PVA/PEO/LD-MCC/KOH (7 g) alkaline polymer electrolyte
membranes with various content of LD-MCC conditioned at 50% RH.
be expected when different LD-MCC loadings were applied in the
ASPE membrane, which led to the different OH diffusion
coefcients. For the concentration of OH in our case, the different
LD-MCC loadings resulted in the different values. This was because
the degree of disrupting the KOH aggregates varied at different LD-
MCC loading levels (section3.2 Morphology and Structure Analy-
ses), which would change the concentration of KOH molecules take
part in the transport of hydroxide ions. Therefore, the different
LD-MCC loadings in the ASPE membrane resulted in the different
diffusion coefcients and concentrations of OH , which led to the
different slopes shown in the decay of CV curve (Fig. 6).
It can be recognized that the stability of the PVA/PEO/LD-MCC5/
KOH (7 g) alkaline polymer electrolyte was limited by a potential of
about +0.9 V on the anodic side and 0.9 V on the cathodic side
(Fig. 6), giving the widest electrochemical stability window of
about 1.8 V. In terms of the conductivity and electrochemical
stability, the high alkali tolerance ASPE membrane developed in
this work exhibits a comparable performance relative to the
reported results in recent literatures (Table S1 in the supplemen-
tary data). It is a suitable candidate for application in alkaline
Znair battery.
3.3.2. Performance of Zn/ASPE/Air battery
The PVA/PEO/LD-MCC/KOH alkaline polymer electrolyte lms
are applied to the Zn-Air battery. The discharge curve of Zn-Air
battery with PVA/PEO/LD-MCC5/KOH (7 g) membrane at room
temperature with the C/10 discharge rate is shown in Fig. 7. The
electric capacity of Zn-air battery with PVA/PEO/LD-MCC5/KOH
(7 g) polymer electrolyte membrane exhibits high specic capacity
of 1339.5mAh/g. The discharge curve is roughly divided into three
processes. At the rst stage of 0- 25 min, the voltage falls abruptly
to an open-circuit voltage (1.10 V). And then the voltage drops
slowly to 0.55 V within 25510 min. The rate of discharge starts
641
accelerating, which leads to the voltage decline promptly to 0.3 V
within the 510560 min scope. This result demonstrates that the
battery prepared here possesses long discharge time for the
application in alkaline batteries. The assembled Zn-Air battery
with PVA/PEO/LD-MCC5/KOH (7 g) alkaline polymer electrolyte
membrane was installed in the LED light, as the inset shown in
Fig. 7. When positive and negative electrodes were linked with the
LED light, resplendent rays emitted and continued about 35 h.
3.3.3. Mechanical properties
Fig. 8 shows the typical stress-strain curves for the PVA/PEO/
LD-MCC/KOH (7 g) alkaline polymer electrolyte membranes
conditioned at 50% RH with various contents of LD-MCC. For the
alkaline polymer electrolyte without LD-MCC, the membrane
showed a fracture only when strain reached around 50%. After the
introduction of 1 wt%, 5 wt% LD-MCC, both the Youngs modulus
and the elongation at break were increased remarkably (Fig. 8B). It
is an indication of the reinforced strength and increased exibility
for LD-MCC added PVA/PEO alkaline polymer membrane. This
could be attributed to the relatively good dispersion of LD-MCC in
the polymeric matrix (as shown in Fig. 2) and the interfacial
interactions between LD-MCC and PVA/PEO matrix. However,
when 10 wt% LD-MCC was added, the mechanical properties
decreased because of the aggregation of excess LD-MCC. Even
though, the mechanical properties were better than that of PVA/
PEO/KOH (7 g) membrane (Fig. 8B). Therefore, the addition of LD-
MCC not only improved the ionic conductivity but also enhanced
the mechanical properties of the membranes.
4. Conclusions
A novel alkaline solid polymer electrolyte membrane with high
alkali tolerance, signicantly improved ionic conductivity and
642 Y. Zhang et al. / Electrochimica Acta 220 (2016) 635642
mechanical properties was prepared via a facile solution-casting
approach. LD-MCC, the functional component in ASPE membrane,
served as KOH stabilizer, hydrophilicity agent and OH transmis-
sion media. The ionic conductivity was found to be greatly
dependent on the KOH concentration, water content and the
LD-MCC percentage. Remarkable improvements in ionic conduc-
tivity (from 0.018 S cm 1 to 0.153 S cm 1) and mechanical proper-
ties (3-fold increase in tensile strength from 0.28 MPa to 0.76 MPa)
at room temperature were achieved when PVA(2.4 g)/PEO(0.6 g)-
based matrix was incorporated with 7 g KOH and 5 wt% LD-MCC.
Distinct SEM morphology of ASPE membrane after the introduc-
tion of LD-MCC demonstrated the internal structural character-
istics. EDX, WAXD and TGA further revealed the roles of LD-MCC in
the ionic conductivity of ASPE membrane. Key features in
membranes were described by a schematic diagram to illustrate
the relationship between micro-structure and ionic conductivity.
The high potential for the performance improvement of ASPE
membrane via pretreated microcrystalline cellulose was demon-
strated.
Acknowledgments
We thank Jinan Science & Technology Bureau Science &
Technology Youth-Star Program (2013034), 2015 Shandong
Province Development Plan of Young Teacher, National Natural
Science Foundation of China (51403111) and National Natural
Science Foundation of Shandong Province (ZR2013EMQ005) for
nancial support.
Appendix A. Supplementary data
Supplementary data associated with this article can
be found, in the online version, at http://dx.doi.org/10.1016/j.
electacta.2016.10.103.
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