Electrochimica Acta 155 (2015) 6168

Contents lists available at ScienceDirect

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

Enhancement of electrochemical performance with Zn-Al-Bi layered

hydrotalcites as anode material for Zn/Ni secondary battery
Zheng Zhang a,b , Zhanhong Yang a, * , Jianhang Huang a,b , ZhaoBin Feng a,b , Xiaoe Xie a,b
a
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
b
Innovation base of energy and chemical materials for graduate students training, Central South University, Changsha 410083, China

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

Article history: Bi-doped Zn-Al layered double hydroxides (Zn-Al-Bi LDH) are prepared by the constant pH hydrothermal
Received 26 August 2014 method and proposed as a novel anodic material in Zn/Ni secondary cells. The Fourier transform infrared
Received in revised form 21 December 2014 spectra (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) images reveal that the as-
Accepted 23 December 2014
prepared samples are well-crystallized and hexagon layer structure. The electrochemical performances
Available online 26 December 2014
of the Zn-Al-Bi LDH were analyzed by cyclic voltammetry, tafel plot, electrochemical impedance
spectroscopy (EIS) and galvanostatic charge-discharge tests. Compared with Zn-Al LDH, Zn-Al-Bi LDH
Keywords:
with different Zn/Al/Bi molar rations, especially the sample of Zn/Al/Bi = 3:0.8:0.2 (molar ration) have
Zn/Ni secondary battery
Zn-Al-Bi LDH
higher discharge capacity and more stable cycling performances. Cyclic voltammograms clearly
electrochemical performance illuminated that the Zn-Al-Bi LDHs could decrease polarization, maintain the electrochemical activity,
cyclic voltammograms and enhance the discharge capacity of Zn-Al LDH. This battery can undergo at least 800 charge-discharge
hydrothermal method cycles at constant current of 1C without dendrite and short circuits. The discharge capacity of Zn-Al-Bi
LDH after the 800th cycle remains about 380 mAh g
1 and the hexagonal crystal structure have no much
changed after cycles.
2014 Elsevier Ltd. All rights reserved.

1. Introduction So far, a large variety of additives, such as Ca(OH)2 [12,22], In

The Zn/Ni secondary battery is a promising candidate for
secondary alkaline storage cells. It possesses good cell perfor-
mance: high specic energy density, high power density, high
open-circuit-voltage, low cost and low toxicity [14]. However, Zn/
Ni batteries have not penetrated commercial markets. A funda-
mental problem is the short and unpredictable lifetime of the Zn
electrodes when it is subjected to charge-discharge cycling. This
problem has been traced to the dissolution of active materials,
shape change of the Zn electrode and the formation of Zn dendrite
[511]. Consequently, the Zn/Ni cells have not received much
attention for application. So far, many attempts have been made to
enhance the performance of the cells. Up to now, most of
researchers have pay attention to the additives to the ZnO
electrode and electrolyte. Hence, many attempts have been made
to conquer the problems, but majority of researches have focused
on the electrolyte, modication of ZnO and additives in the
electrodes [1221].
* Corresponding author. Tel.: +86 731-88879616; fax: +86 731-88879616.
E-mail address: zhongnan320@gmail.com (Z. Yang).
(OH)3 [2,7,23], BaO [24], were used in zinc electrodes to overcome
the problems mentioned above and an obvious enhancement has
been obtained. Among all these additives, compounds of bismuth
are thought to be the important component of electrodes because
these compounds have a suppressive effect on H2 formation,
decrease shape change and self-discharge, resulting in a more
uniform current density distribution and improved cell lifetimes
[5,25,26]. Nevertheless, Bi compounds additives are usually
physically mixed with ZnO in the ZnO electrode. This approach
cannot provide homogeneous mixture between the additives and
ZnO particles, so that the efciency of the additive is relatively low.
LDHs, or hydrotalcite-like compounds, are a class of anionic
clays consisting of positively charged metal hydroxide layers with
charge-compensating anions located in the interlayer, with the
general formula [M(II)1-xM(III)x(OH)2]x+(An
)x/nmH2O, while M
(II) is a divalent metal cation, M(III) is atrivalent metal, and An- is
an anion. LDHs has been applied in many aspects, including
catalysts, ion conductivity, adsorbents and anion exchangers [27
29]. Zn-Al-hydrotalcite have been directly applied to the zinc
electrode by our previous work [2,6,30,31,32], and the results show
Zn-Al-hydrotalcite as anodic materials of Zn/Ni batteries exhibits
good reversibility, superior electrochemical cycling stability and
more excellent utilization ration in the alkaline solution compared

http://dx.doi.org/10.1016/j.electacta.2014.12.145
0013-4686/ 2014 Elsevier Ltd. All rights reserved.
62 Z. Zhang et al. / Electrochimica Acta 155 (2015) 6168
with the ZnO. However, Zn-Al-hydrotalcite suffer low conductivity
and largely suppress the electron transfer for electrode reaction
[2]. Therefore, in order to enhance its electrochemical perform-
ances, it should have further modication on Zn-Al LDH. In the
present work, Zn-Al-Bi LDH has been proposed as zinc electrode
materials and the electrochemical properties were studied in
details.
2. Experimental
2.1. The preparation of Zn-Al-Bi-hydrotalcitie
The typical experimental operation was as follows: Zinc,
Aluminum nitrates (AR, Tianjin City Guang Fu Fine Chemical
Institute) were dissolved in a certain volume of deionized water,
Bismuth nitrate (AR, Shanghai City Jin Shan Ting Xin Chemical
Institute) was dissolved in concentrated nitric acid solution,
keeping the Zn/Al/Bi molar ratio of 3:1:0, 3:0.6:0.4, 3:0.8:0.2 and
3:0.9:0.1; then the above two saline solution and a mixture
containing NaOH (2 mol L-1) and Na2CO3 (0.5 mol L-1) (AR, Tianjin
City Guang Fu Fine Chemical Institute) were added simultaneously
to a three-necked ask at a speed of 1 drop s-1, keeping the total
metal ion concentration of 1.0 mol L-1, which contained 100 ml
deionized water and was under the protection of inert gas nitrogen.
The process was carried out under vigorous stirring at 45  C, and
appropriate amount of NaOH solution was added to keep the pH
value of 10. After stirring for 30 min, the mixture was poured into
Teon-lined autoclave, and then kept for 10 h under 120  C. The
product cooled to room temperature was ltered and washed for
several times with deionized water and ethyl alcohol until the pH
reached 7, dried for 24 h under 60  C and ground to ne powder.
Then the product of Zn-Al-Bi LDH powders were collected and
packed in a PE bag for further examination and use.
2.2. The characterization of the Zn-Al-Bi LDH samples
The XRD patterns of as-prepared Zn-Al-Bi LDH and Zn-Al LDH
powder were determined by X-ray diffraction analysis diffractom-
eter (Rigaku D/max III with Cu Ka radiation) at 40 kV and 80 mA.
The scanning rate of XRD was 4 /min. The morphologies of Zn-Al-
Bi LDH were observed by scanning electron microscopy (SEM, JSM-
6360LV). Fourier transform infrared spectra (FT-IR) of the samples
were conducted on a Nicolet Nexus-670 FT-IR spectrometer (as KBr
discs, with wave number 4004000 cm-1, resolution 0.09 cm-1, and
the weight of measured sample is 2 mg).
2.3. The preparation and electrochemical measurements of the Zn-Al-
Bi LDH electrodes
The Zn-Al-Bi LDH electrodes were prepared by incorporation
slurries containing 85 wt. % Zn-Al-Bi LDH, 10 wt. % acetylene black
and 5 wt. % additives of polytetrauoroethylene (PTFE, 60 wt. %, in
diluted emulsion). Copper mesh (1.0 cm  1.0 cm in size) was
served as the current collector and the Zn-Al-Bi-LDH electrodes
were roll-pressed to a thickness of 0.2 mm. Then, the obtained Zn-
Al-Bi LDH electrodes were dried at 60  C under vacuum. For
comparison, Zn-Al LDH electrodes were also fabricated by the
same way. The positive electrode was the commercial sintered Ni
(OH)2 electrode (Tianjin City Fine Chemical Research Institute)
whose capacity was much larger than Zn-Al-Bi LDH electrode for
making full use of the active material in Zn-Al-Bi LDH electrode.
The electrolyte is solution of 6 M KOH saturated with ZnO. All the
cells were pre-activated for 10 times by the following operations:
The cells were charged at constant current of 0.1 C for 600 min, and
discharged at constant current of 0.2 C to a cut-off voltage of 1.2 V.
A three-electrode cell was assembled for cyclic voltammograms
(CV), Tafel polarization and electrochemical impedance spectros-
copy (EIS), with Hg/HgO electrode served as the reference
electrode, pre-activated pasted zinc electrode as the working
electrode and the sintered Nickel electrode as counter electrode.
The capacity of counter electrode was far higher than that of zinc
electrode. The electrolyte was 6 mol L
1 KOH solution saturated
with ZnO. Before the tests, the cells need to be activated. CV was
carried out on an electrochemical workstation (CHI660D) at room
temperature at a scanning rate of 5 mV s
1 range from -0.95 V to
-1.65 V. Tafel polarization curves were carried out using an
electrochemical workstation (RST-500) at room temperature with
a scanning rate of 0.5 mV s
1 range from -1.3 V to -1.5 V.
Electrochemical impedance spectroscope (EIS) measurements
were performed on a PARSTAT 2273 type electrochemical system
(Princeton, America). The frequency range applied was between
0.01 Hz and 100 KHz with 105 amplitude of 10 mV. The galvano-
static charge-discharge tests were performed on a BTS-5 V/10 mA
battery-testing instrument (Neware, China) at room temperature.
During the cycling process, the cells were charged at 1 C for 60 min
and discharged at 1 C down to 1.2 V cut-off voltages.
In all the above experiments, the reagents used were A.R. grade
and the electrolyte was prepared with deionized water.
3. Results and discussion
3.1. The structural analysis of Zn-Al-Bi LDH
For the samples of Zn-Al LDH and Zn-Al-Bi LDH with different
Zn/Al/Bi molar ratios, the FT-IR spectra are shown in Fig. 1 . The
broad band around 3444 cm-1 can be ascribed to the OH

stretching mode of the layer hydroxyl groups and the interlayer
water molecules. The O-C-O asymmetric stretching vibration
appears between 1365 and 1508 cm-1. Compared with CO32- of
CaCO3 (1430 cm-1), there is a considerable lower shifted absorption
peak at 1365 cm-1, shows that there was an intercalation between
CO32- and interlayer H2O through the strong hydrogen bonding.
The lower wave number bands at 400700 cm-1 is due to LDH
lattice vibrations (Zn-O, Al-O, Bi-O). The bands at 791 cm-1, 554 cm-
1
and 431 cm-1 can be assigned to the Al-O and Bi-O stretching
modes. These Al-O peaks of Zn-Al-Bi LDH are weaker than those of
Zn-Al LDH. As aluminum atomic radius (1.82 ) and bismuth
atomic radius (1.63 ) are not signicant and they are both trivalent
ions, partial aluminum atoms in lattice can be replaced by bismuth
[(Fig._1)TD$IG]
Fig. 1. FT-IR spectra of Zn-Al LDH and different Zn/Al/Bi molar rations of Zn-Al-Bi
LDH A: Zn/Al/Bi = 3:1:0; B: Zn/Al/Bi = 3:0.6:0.4; C: Zn/Al/Bi = 3:0.8:0.2; D: Zn/Al/
Bi = 3:0.9:0.1.
 Z. Zhang et al. / Electrochimica Acta 155 (2015) 6168
[(Fig._2)TD$IG]
Fig. 2. XRD patterns of Zn-Al LDH and different Zn/Al/Bi molar rations of Zn-Al-Bi
LDH A: Zn/Al/Bi = 3:1:0; B: Zn/Al/Bi = 3:0.6:0.4; C: Zn/Al/Bi = 3:0.8:0.2; D: Zn/Al/
Bi = 3:0.9:0.1.
atoms. The result of FT-IR spectra indicates that the Bi element
have been successfully inserted into the Zn-Al LDH lattice.
The XRD patterns of Zn-Al LDH and Zn-Al-Bi LDH samples with
different Zn/Al/Bi mole ratios are shown in Fig. 2. As shown in
Fig. 2, it can be seen that Zn-Al-Bi LDH samples have strong peaks
at 2u = 11.7, 23.56 , 34.56 and 61.56 corresponding to (0 0 3),
[(Fig._3)TD$IG]
Fig. 3. The typical SEM image of Zn-Al LDH and different Zn/Al/Bi molar rations of Zn-Al-Bi LDH A:Zn/Al/Bi = 3:1:0; B: Zn/Al/Bi = 3:0.6:0.4; C: Zn/Al/Bi = 3:0.8:0.2; D: Zn/Al/
Bi = 3:0.9:0.1.
63
(0 0 6), (0 0 9) and (11 0) planes, respectively. It is clear that Zn-Al-
Bi LDH has hexagonal structure reported in the literature (JCPDS
No. 05-0669), which almost has no change with Zn-Al LDH in the
diffraction peaks position. All of the samples exhibit the
characteristic diffraction peak of layered hydrotalcite-like materi-
als, indicating that the bismuth does not destroy layered structure
of the LDH, whereas a gradual decline in the intensity of (0 0 3)
reection peak and a signicant broadening of (0 0 9) reection
was observed in the patterns of Zn-Al-Bi LDH. It can be noted that,
only in the sample with the highest content of Bi (Zn:Al:
Bi = 3:0.6:0.4) the presence of Bi2O2CO3 can be observed (black
stars in Fig. 2B), denoting that some Bi was not incorporated in the
LDH structure. It is well known that Bi(NO3)3 is an unstable weak
acidity compound, and partial Bi3+ was hydrolyzed to Bi2O2CO3 in
the process of precipitation, which co-exists with Zn-Al-Bi LDH.
The highest diffraction peak appears at 2u = 11.71, suggesting the
Zn-Al-Bi LDH is a highly crystallized hydrotalcite-like compound
and has a typical hexagonal crystal structure.
The typical SEM images of Zn-Al LDH and different Zn/Al/Bi
mole ratios of Zn-Al-Bi LDH are presented in Fig. 3. It can be
observed that all three kinds of Zn-Al-Bi LDH samples appear with
circinal or hexagonal platelet-like structures that are similar to the
typical structure of Zn-Al LDH [30]. This result shows that
appropriate addition of Bi do not destroy the lattice structure of
active material [31,33]. The particle size is about 200400 nm.
Based on the analysis above, Zn-Al-Bi LDH is produced successfully
through hydrothermal method.
The molecular structure of Zn-Al LDH and Zn-Al-Bi LDH from
different perspectives is represented in Fig. 4. As shown in Fig. 4, a
64 Z. Zhang et al. / Electrochimica Acta 155 (2015) 6168
[(Fig._4)TD$IG]
Table 1
The data for the Cyclic voltammograms for zinc electrodes with Zn-Al LDH and
different Zn/Al/Bi molar rations of Zn-Al-Bi LDH A: Zn/Al/Bi = 3:1:0; B: Zn/Al/
Bi = 3:0.6:0.4, C: Zn/Al/Bi = 3:0.8:0.2, D: Zn/Al/Bi = 3:0.9:0.1.

Anode Anodic Anodic Cathode Cathode Ox-Red

material peak peak peak peak potential
positiona height positiona height (A) differencea (V)
(V) (A) (V)
A -1.2476 0.4477 -1.4634 -0.1297 0.2158
B -1.2845 0.4892 -1.4475 -0.1926 0.1630
C -1.2954 0.5577 -1.4346 -0.1853 0.1392
D -1.2872 0.3982 -1.4515 -0.1684 0.1643
a
Potential vs. (Hg/HgO)

from these curves are given in Table 1. The redox peaks are ascribed
to the reduction of ZnO and the oxidation of Zn. As observed from
Table 1, the cathodic peaks potential of zinc electrodes containing
the Zn-Al LDH (code A), Zn-Al-Bi LDH with Zn:Al:Bi = 3:0.6:0.4
(code B), Zn-Al-Bi LDH with Zn:Al:Bi = 3:0.8:0.2 (code C), Zn-Al-Bi
LDH with Zn:Al:Bi = 3:0.9:0.1 (code D) are -1.4634 V, -1.4475 V,
-1.4346 V and -1.4515 V, respectively. The cathodic peak reects the
charge process of Zn/Ni secondary battery. In the process of
activating, the elemental of Bi will precipitation priority reduction
from Bi3+ and keep the metallic Bi in the cycling process. So the Bi
element don't participate in cycling reaction. During the charge
process, zinc ions reduced into zinc metal after free out from the
structure of the hydrotalcite. The reaction can be represented by
Eqs. (1),(2) and (3) [6,30].
[Zn1+x Alx (OH)2]x+(CO3)x/2n2n
mH2O ! (1-x)Zn2+ + xAl3+ + 2OH
+
x/2nCO32n- (1)

Fig. 4. The structure of Zn-Al-Bi LDH before activate.

Zn2+ + 4OH- ! Zn(OH)42- (2)

part of aluminum atoms can be replaced by bismuth atoms, the
structure of LDH remains the same. These analysis results indicate
that the aluminum atoms in lattice can be replaced by bismuth
atoms successfully and the bonds are not damaged.
3.2. The cyclic voltammograms of Zn electrodes
To investigate electrochemical properties of the Zn-Al LDH and
Zn-Al-Bi LDH, cyclic voltammetry were carried out and the
recorded CV curves are shown in Fig. 5. The curves should be
associated with Zn2+/Zn redox couple and the reaction have been
reported by us [2,6]. The electrochemical kinetic parameters derive
[(Fig._5)TD$IG]
Zn(OH)42
+ 2e ! Zn + 4OH- (3)
Generally speaking, a more positive potential, means a higher
electrochemical kinetics of reduction process, that is to say,
electrode B, C and D shows better electrochemical kinetics, and the
charge process is more effective and rapid [4].
The cathodic process reects the charge process of Zn/Ni
secondary battery, more positive peak potential means the lower
charge platform voltage in galvanostatic charge and discharge test
[34]. The anodic process reects the discharge process of Zn-Ni
secondary battery. Their corresponding anodic peaks potential at
-1.2476 V, -1.2845 V, -1.2954 V and -1.2872 V are also observed in
Fig. 5. During the discharge process, zinc metal is oxidized into
bivalent zinc ions, and then it enter into the structure of
hydrotalcite. The reaction can be represented by Eqs. (4) and (5).
Zn + 4OH- ! Zn(OH)42- + 2e (4)

1-x)Zn2+ + xAl3+ + 2OH- + x/2nCO32n- + mH2O ! [Zn1-xAlx (OH)2]x

Fig. 5. Cyclic voltammograms for zinc electrodes with Zn-Al LDH and different Zn/
Al/Bi molar rations of Zn-Al-Bi LDH A: Zn/Al/Bi = 3:1:0; B: Zn/Al/Bi = 3:0.6:0.4; C: Zn/
Al/Bi = 3:0.8:0.2; D: Zn/Al/Bi = 3:0.9:0.1.
+
(CO3)x/2n2n-mH2O (5)
Compared with zinc electrode A, B and D, zinc electrode C
shows the highest anodic peak current, the largest anodic peak
area and the lowest anodic peak potential. The increase in anodic
peak area and anodic peak current means that zinc electrode C
possesses the highest electrochemical activity, and can provide
more discharge capacity than that of other zinc electrodes. The
better electrochemical activity is owing to the bismuth additive in
the Zn-Al-Bi LDH. The mechanism of Bi3+ reduced to Bi metal in
KOH electrolyte is similar to the reported Bi2O3 in hydroxide
electrolyte [3537]. The reduction potential of Bi (III) to Bi metal is
 Z. Zhang et al. / Electrochimica Acta 155 (2015) 6168
[(Fig._6)TD$IG]
Fig. 6. The schematic diagram of Zn-Al-Bi LDH after activate.
around -0.87 V. During the reduction process, the following
reaction takes place
BiO2 - ! BiO2(ads) -
(6)
BiO2(ads) - + e - ! BiO2(ads)2- (7)
disproportionation
2BiO2ads
4OH
Biads
0
2H2 O 3BiO2ads 2
$ (8)
Biads 0 ! Bimetal (9)


The majority of BiO ions are in the ionic state, which
undergoes the following reactions to form metallic Bi. The
electrode potential of Bi (III)/Bi (-0.87 V) is more positive than
that of Zn(OH)42-/Zn(-1.99 V) in the alkaline solution.
Zn(OH)42- ! Zn + 4OH- EF = -1.99 V (10)
3+
In the process of activating, the Bi will be rst reduced to Bi
metal, which forming a conductive network and improving the
conductivity of the LDHs as depicted in Fig. 6. In addition, Bi
element has high overpotential of hydrogen evolution, so it will
inhibits the production of hydrogen and decreases self-discharge.
The different peak area and peak current of the Zn-Al-Bi LDH
electrodes presented in the Fig. 5 is attributed to the concentration
of bismuth metal in the three kinds of hydrotalcite. This
phenomenon can be explained as that less addition amount of
Bi such as electrode D is not so effective to affect the
electrochemical performance. However, due to the atomic radius
of Bi is smaller than that of Al, an excessive Bi additive leads to
disproportion of lattice and destroy the layer structure. In addition,
partial Bi3+ hydrolyze to Bi2O2CO3 in the process of preparation,
which co-exists with Zn-Al LDH. So it can decrease the direct
contact of the zinc atoms with electrolyte, result the poor
electrochemical activity.
3.3. The Tafel polarization curves of zinc electrodes
For understanding the changes of corrosion protection proper-
ties of Zn-Al-Bi LDH on the performance of zinc electrode, the Tafel
polarization experiments are carried out. Fig. 7 shows the Tafel
curves of the zinc electrodes, whose Zn:Al:Bi (molar ratio) is
3:0.6:0.4, 3:0.8:0.2 and 3:0.9:0.1 are coded as B, C and D electrodes,
respectively. The plots show similar features, and the cathodic
reaction is shown in Eq. (11), while the corrosion reaction can be
represented by Eq. (12).
Zn(OH)42- + 2e ! Zn + 4OH- (11)
65
[(Fig._7)TD$IG]
Fig. 7. Tafel polarization curves for zinc electrodes with Zn-Al LDH and different Zn/
Al/Bi molar rations of Zn-Al-Bi LDH A: Zn/Al/Bi = 3:1:0; B: Zn/Al/Bi = 3:0.6:0.4; C: Zn/
Al/Bi = 3:0.8:0.2; D: Zn/Al/Bi = 3:0.9:0.1.
H2O + 2e ! H2 " 2OH- (12)
The electrochemical kinetic parameters derive from these
curves are given in Table 2. The electrochemical kinetic parameters
include corrosion potential (Ecorr), corrosion current density (jcorr),
and inhibition efciency (I.E.%) [15]. The inhibition efciency
expressed as percent inhibition I.E.% is dened as [30]:
I.E.% = (jcorr0 - jcorr)/jcorr  100% (13)
where jcorr0
and jcorr present the corrosion current densities of
electrode A without Bi and electrodes (B, C, D) with Bi addition. As
explained in the Principles of Electrochemistry of Corrosion, Ecorr is
the critical value the corrosion occurs on electrode, and more
negative Ecorr means the larger degree of corrosion. The jcorr means
the corrosion speed, and smaller jcorr implies the better anti-
corrosion property.
Obviously, the inhibition efciency of Zn-Al-Bi LDH electrode
with Zn:Al:Bi = 3:0.8:0.2 is the greatest, and the steady-state
corrosion potential is the most positive. For the sample with Zn:Al:
Bi = 3:0.9:0.1, the less adding amount of Bi which cannot effectively
make hydrogen evolution over-potential shift positively. However,
the hydrogen evolution over-potential of Zn-Al-Bi LDH with Zn:Al:
Bi =3:0.6:0.4 is smaller due to the small radius of the bismuth
element, the excessive Bi additive will make disproportion of
lattice and destroy the layerd structure of Zn-Al LDH. According to
the investigating of mechanism, Bi compounds are irreversibly
reduced to metallic Bi at the activation process, and then exist all
the time in the state of metallic Bi. Metallic Bi can reduce the
contact resistance among Zn-Al LDH particles, provide an electro-
depositing substrate to promote even deposition of zincate, thus
increase overpotential for hydrogen evolution. This conclusion is
accordance with the cyclic voltammograms discussion above.
Table 2
The data for the Tafel curves for zinc electrodes with Zn-Al LDH and different Zn/Al/
Bi molar rations of Zn-Al-Bi LDH A: Zn/Al/Bi = 3:1:0; B: Zn/Al/Bi = 3:0.6:0.4, C: Zn/Al/
Bi = 3:0.8:0.2, D: Zn/Al/Bi = 3:0.9:0.1.
Sample Ecorr (v) jcorr (mA cm
2) I.E.%
A -1.4269 5.09  10-2
B -1.3680 3.88  10-2 23.77
C -1.3555 3.04  10-2 40.27
D -1.3909 4.21 10-2 17.28
 66 Z. Zhang et al. / Electrochimica Acta 155 (2015) 6168
[(Fig._8)TD$IG]
Fig. 8. (a) Nyquist plots of the electrodes with Zn-Al LDH and different Zn/Al/Bi
molar rations of Zn-Al-Bi LDH A: Zn/Al/Bi = 3:1:0; B: Zn/Al/Bi = 3:0.6:0.4; C: Zn/Al/
Bi = 3:0.8:0.2; D: Zn/Al/Bi = 3:0.9:0.1 and (b) equivalent circuit for the electrode.
[(Fig._9)TD$IG]
Fig. 9. Typical galvanostatic charge-discharge curves of Zn/Ni secondary batteries
with Zn-Al LDH and Zn-Al-Bi LDH with different Zn/Al/Bi molar ratio A: Zn/Al/
Bi = 3:1:0; B: Zn/Al/Bi = 3:0.6:0.4, C: Zn/Al/Bi = 3:0.8:0.2, D: Zn/Al/Bi = 3:0.9:0.1.
3.4. The results of electrochemical impedance spectroscopy (EIS)
AC impedance measurements are performed to investigate the
impedance of Zn-Al LDH and Zn-Al-Bi LDH. Fig. 8 (a) shows the
Nyquist plots of the electrodes with Zn-Al LDH and Bi-doped Zn-Al
LDH, including one depressed semicircles and one slope. The
semicircle in the high frequency region is attributed to the charge-
transfer resistance, and the slope in the low frequency region is
caused by the diffusion of zincate in the electrode. The equivalent
circuit for the electrode is shown in Fig. 8 (b), where CPE designates
the constant-phase element, Re is the total ohmic resistance, which
includes the resistance of the electrolyte, current collector, etc., Rct
is the charge-transfer resistance and Zw is the Warburg impedance.
Calculating the diameter of the semicircle of the curves in Fig. 8 (a),
it can be found that the Zn-Al LDH shows the largest charge-
transfer resistance value (about 25 V cm2), while the Zn-Al-Bi LDH
composites with different Zn/Al/Bi mole ratios exhibit the much
smaller charge-transfer resistance (B = 7.83 V cm2, C = 4.63 V cm2,
D = 15.32 V cm2). It indicates that the addition of bismuth element
could decrease the value of charge transfer resistance, which plays
a critical role in the electrode reaction kinetics. A small charge-
transfer resistance indicates that the related electrochemical
reaction is easier and leads to a decrease in electrochemical
polarization of zinc electrodes and an increase in the utilization of
active material. Such a small charge-transfer resistance is ascribed
to the Bi element. In the process of activating, the Bi3+ will be rst
reduced to Bi metal, which forming a conductive network and
improving the conductivity in layered structure and thus results in
faster electron transportation. Almost the same Warburg imped-
ance of both indicates that the addition of bismuth does not affect
the diffusion between the solution and the electrode. These results
are corresponding with the CV curves in Fig. 5, the diminutive
resistance of Zn-Al-Bi LDH illustrates the lower charge plateau
voltage and the higher discharge plateau voltage.
3.5. The properties of galvanostatic charge and discharge
Fig. 9 displays the charge/discharge curves of Zn/Ni cells with
the Zn-Al LDH and Zn-Al-Bi LDH samples at the 50th cycle. The
overall electrode reaction can be described as Eqs. (14) and (15).
Charge process:
Zn(OH)42- + 2e ! Zn + 4OH- (14)
Discharge process:
[(Fig._10)TD$IG]
Fig. 10. Cycling stability of Zn-Al LDH and Zn-Al-Bi LDH with different Zn/Al/Bi
molar ratio A: Zn/Al/Bi = 3:1:0; B: Zn/Al/Bi = 3:0.6:0.4, C: Zn/Al/Bi = 3:0.8:0.2, D: Zn/
Al/Bi = 3:0.9:0.1.
 Z. Zhang et al. / Electrochimica Acta 155 (2015) 6168
[(Fig._1)TD$IG]
Fig. 11. SEM pattern of Zn-Al LDH (a) and Zn-Al-Bi LDH (b) electrodes after complete discharge over 800 cycles.
Zn + 4OH- ! Zn(OH)42- + 2e (15)
The Zn/Ni cells with the Zn-Al LDH show relatively higher
charge midpoint voltage (1.89 V) and lower discharge midpoint
voltage (1.79 V). The Zn-Al-Bi LDH with mole ratio of
3:0.9:0.1 delivers charge midpoint voltage 1.87 V and discharge
midpoint voltage 1.81 V as well. The increase of Bi content can
enhance conductivity of Zn-Al LDH. As a result, charge midpoint
voltage of the Zn/Ni cells descends. Therefore, Zn-Al-Bi LDH with
mole ratio of 3:0.8:0.2 and 3:0.6:0.4 show charge midpoint voltage
1.83 V, 1.84 V, respectively. The decrease of charge voltage can
result in an increase of charge efciency and utilization of active
material in the anodes. The main reason can be summarized that
the Bi element provides good electrical conductivity in the Zn
electrodes and decreases internal resistance of the Zn electrodes,
which is demonstrated in part of EIS. Besides, due to the higher
hydrogen evolution over-potential of bismuth metal in the Zn-Al-
Bi LDH, it can provide an excellent ability of corrosion protection
and can decrease the polarization of zinc electrodes, which is
accordance with the results of CV and tafel section. In addition, the
discharge voltage is an important parameter for batteries. Higher
discharge voltage associates with higher specic power and better
performance in the battery discharge process. From Fig. 9b, it can
be seen that the Zn/Ni secondary battery with Zn-Al-Bi LDH anodes
have much higher and atter discharge platform compared with
the Zn-Al LDH anode. Compared with batteries B and D, battery C
shows the highest discharge plateau voltage. This means Zn-Al-Bi
LDH with Zn:Al:Bi = 3:0.8:0.2 shows the best electrochemical
performances.
3.6. The cycle performance analysis of Zn-Al-Bi LDH
Fig. 10 illustrates the electrochemical cyclic behaviors of the Zn-
Al LDH and Zn-Al-Bi LDH. The highest discharge capacity of the Zn-
Al LDH is about 375 mAh g-1 at the 105th cycle, and then it suffers
from rapid capacity fade. At the 800th cycle, the discharge capacity
decreases to 12 mAh g-1 with a retention of 33.9%. In comparison
with the Zn-Al LDH sample, it can be found that all the three kinds
of Zn-Al-Bi LDH electrodes show more excellent cycle stability than
the Zn-Al LDH in the 800 cycles.
The rst cycle discharge capacity of Zn-Al-Bi LDH anodes (molar
ratio: 3:0.6:0.4, 3:0.8:0.2, 3:0.9:0.1) are 386 mAhg-1, 380 mAhg-1
and 354 mAhg-1, respectively. Meanwhile, it can be found that the
initial discharge capacity of Zn-Al-Bi LDH anodes descend with the
increasing of bismuth content. For comparison, all Zn-Al-Bi LDH
samples show more excellent cycle stability and capacity retention
ratio of 89.49%, 98.35% and 91.01% in the 800th cycle, respectively.
It illustrates that the discharge capacity and cycling stability of Zn-
67
Al-Bi LDH material are superior to the corresponding performances
of Zn-Al LDH.
In order to illustrate the inuence of Zn-Al-Bi LDH on the cycle
performance of Zn/Ni cell, the typical SEM images of Zn-Al-Bi LDH
(Zn:Al:Bi = 3:0.8:0.2) and Zn-Al LDH electrodes after 800 charge-
discharge cycles are shown in Fig. 11. As can be seen, after
800 cycles, the typical hexagonal crystal structure of Zn-Al LDH
had been elongated and the top changed into the acicular form,
namely Zn dendrites. The Zn dendrite readily penetrates the
separators and resulted in the interior short circuit, so it is one
important cause for the aggravation of cell performance. For
comparison, the morphology of Bi-doped electrode after 800 cycles
is shown in Fig. 11. Contrasted with the Zn-Al LDH, it is clear that
there is less Zn dendrite formed and the hexagonal crystal
structure did not essentially change after the charge-discharge
cycles. The morphology retention can stabilize the electrochemical
performance of active substance to a certain extent. This superior
cycle performance is owed to the typical layer structure of LDHs
and the existence of bismuth element. During the charge process,
zinc ions and bismuth ions are reduced into zinc metal and
bismuth metal, respectively. Element Al exists in the form of oxides
[Al2O3/Al(OH)3] in the electrode [30]. Because the standard
electrode potential of Al(OH)3/Al (-2.31 V) is more negtive than
that of Zn(OH)42-/Zn (-1.99 V) and Bi (III)/Bi (-0.87 V) in the alkaline
solution. According to our previous research, in the two-
dimensional layered and structures, the framework effect of
aluminum ions can promote the discharge products formation of
hydrotalcite structure again. In the discharge process, most of Zn
metal is oxidized into Zn-Al-Bi LDH. It can reduce overgrowth of
zinc grain, such as moss and dendrites. However, there are some of
Zn metal is oxidized into the byproduct ZnO [6,38]. ZnO has
dendrite growth in charge-discharge process due to its high
solubility in alkali liquor. On the other hand, the zinc electrode
expanded during charge/discharge process. Compared with Zn-Al
LDH, after the process of activating, the Bi metal could form a
conductive network and improving the conductivity in layered
structure, which lead to a relatively stable discharge voltage and
higher discharge capacity. In addition, the corrosion-inhibiting
additives of bismuth metal have hydrogen evolution over-
potential, which inuences the hydrogen overvoltage of zinc
anode [39,40] and decrease self-corrosion and shape change of zinc
electrodes. Consequently, the plasticity and creep resistance of
active materials had been enhanced substantially.
4. Conclusions
Zn-Al-Bi LDH prepared by hydrothermal method remains the
hexagon layer structure, and shows better electrochemical
68 Z. Zhang et al. / Electrochimica Acta 155 (2015) 6168
performances compared with Zn-Al LDH as anodic active material.
Cyclic voltammograms and Tafel tests show that after doped of Bi
element, it can effective improve the electrochemical activity of
Zn-Al LDH, decrease the polarization and charge voltage of Zn-Al
LDH. The Zn-Al-Bi LDHs with different Zn/Al/Bi molar ration,
especially the sample of Zn/Al/Bi = 3:0.8:0.2 (molar ration)
employed as anode materials exhibit a better electrochemical
performance compared with Zn-Al LDH. The specic capacitance of
Zn-Al-Bi LDH is calculated and reaches 380 mAh g-1 and the
capacity retention ratio can reach 98.35% after 800 charge-
discharge cycles. These results provide important insights for
develop a novel active materials with higher discharge capacity,
good stability in Zn/Ni secondary batteries.
Acknowledgments
This work was supported by the Natural Science Foundation of
China (no. 21371180), Science and technology project of Changsha
city (no. K1303015-11) and Specialized Research Fund for the
Doctoral Program of Higher Education(no. 20130162110018).
References
[1] J. Yang, Y.F. Yuan, H.M. Wu, Y. Li, Y. Chen, S. Guo, Preparation and
electrochemical performances of ZnO nanowires as anode materials for Ni/
Zn secondary battery, Electrochimica Acta 55 (2010) 70507054.
[2] X. Fan, Z. Yang, W. Long, Z. Zhao, B. Yang, The preparation and electrochemical
performance of In (OH)3 coated Zn-Al-hydrotalcite as anode material for ZnNi
secondary cell, Electrochimica Acta 92 (2013) 365370.
[3] S.H. Lee, C.W. Yi, K. Kim, Characteristics and Electrochemical Performance of
the TiO2-Coated ZnO Anode for NiZn Secondary Batteries, The Journal of
Physical Chemistry C 115 (2010) 25722577.
[4] M. Ma, J.P. Tu, Y.F. Yuan, X.L. Wang, K.F. Li, F. Mao, Z.Y. Zeng, Electrochemical
performance of ZnO nanoplates as anode materials for Ni/Zn secondary
batteries, Journal of Power Sources 179 (2008) 395400.
[5] Y.F. Yuan, L. Yu, H.M. Wu, J. Yang, Y. Chen, S. Guo, J.P. Tu, Electrochemical
performances of Bi based compound lm-coated ZnO as anodic materials of
NiZn secondary batteries, Electrochimica Acta 56 (2011) 43784383.
[6] X. Fan, Z. Yang, R. Wen, B. Yang, W. Long, The application of Zn-Al-hydrotalcite
as a novel anodic material for NiZn secondary cells, Journal of Power Sources
224 (2013) 8085.
[7] D. Zeng, Z. Yang, S. Wang, X. Ni, D. Ai, Q. Zhang, Preparation and
electrochemical performance of In-doped ZnO as anode material for NiZn
secondary cells, Electrochimica Acta 56 (2011) 40754080.
[8] Q.C. Horn, S.H. Yang, Morphology and spatial distribution of ZnO formed in
discharged alkaline Zn/MnO2 AA cells, Journal of The Electrochemical Society
150 (2003) A652A658.
[9] S. Szpak, C. Gabriel, The Zn-KOH System: The Solution-Precipitation Path for
Anodic ZnO Formation, Journal of The Electrochemical Society 126 (1979)
19141923.
[10] M. Minakshi, D. Appadoo, D.E. Martin, The anodic behavior of planar and
porous zinc electrodes in alkaline electrolyte, Electrochemical and Solid-State
Letters 13 (2010) A77A80.
[11] M. Minakshi, M. Ionescu, Anodic behavior of zinc in Zn-MnO2 battery using
ERDA technique, International journal of hydrogen energy 35 (2010) 7618
7622.
[12] Y.F. Yuan, J.P. Tu, H.M. Wu, Y. Li, D. Shi, X. Zhao, Effect of ZnO nanomaterials
associated with Ca (OH)2 as anode material for NiZn batteries, Journal of
power sources 159 (2006) 357360.
[13] Y.F. Yuan, J.P. Tu, H.M. Wu, B. Zhang, X. Huang, X.B. Zhao, Preparation,
characteristics and electrochemical performance of Sn6O4(OH)4-coated ZnO
for ZnNi secondary battery, Electrochemistry communications 8 (2006) 653
657.
[14] R. Wen, Z. Yang, X. Fan, Z. Tan, B. Yang, Electrochemical performances of ZnO
with different morphology as anodic materials for Ni/Zn secondary batteries,
Electrochimica Acta 83 (2012) 376382.
[15] W. Long, Z. Yang, X. Fan, B. Yang, Z. Zhao, J. Jing, The effects of carbon coating on
the electrochemical performances of ZnO in NiZn secondary batteries,
Electrochimica Acta 105 (2013) 4046.
[16] C.C. Yang, W.C. Chien, C.L. Wang, C.Y. Wu, Study the effect of conductive llers
on a secondary Zn electrode based on ball-milled ZnO and Ca(OH)2 mixture
powders, Journal of Power Sources 172 (2007) 435445.
[17] J. Wu, J.P. Tu, Y.F. Yuan, M. Ma, X.L. Wang, L. Zhang, R. Li, J. Zhang, Ag-
modication improving the electrochemical performance of ZnO anode for Ni/
Zn secondary batteries, Journal of Alloys and Compounds 479 (2009) 624628.
[18] J. Zhu, Y. Zhou, Effects of ionomer lms on secondary alkaline zinc electrodes,
Journal of power sources 73 (1998) 266270.
[19] R. Shivkumar, G.P. Kalaignan, T. Vasudevan, Studies with porous zinc
electrodes with additives for secondary alkaline batteries, Journal of power
sources 75 (1998) 90100.
[20] Y. Cho, G. Fey, Surface treatment of zinc anodes to improve discharge capacity
and suppress hydrogen gas evolution, Journal of Power Sources 184 (2008)
610616.
[21] Z. Zhang, Z. Yang, R. Wang, Z. Feng, X. Xie, Q. Liao, Electrochemical performance
of ZnO/SnO2 composites as anode materials for Zn/Ni secondary batteries,
Electrochimica Acta 134 (2014) 287292.
[22] R. Wang, Z. Yang, B. Yang, X. Fan, T. Wang, A novel alcohol-thermal synthesis
method of calcium zincates negative electrode materials for NiZn secondary
batteries, Journal of Power Sources 246 (2014) 313321.
[23] S. Wang, Z. Yang, L. Zeng, Effect of surface modication with In(OH)3 on
electrochemical performance of calcium zincate, Journal of the
Electrochemical Society 156 (2009) A18A21.
[24] Y. Zheng, J. Wang, H. Chen, J. Zhang, C. Cao, Effects of barium on the
performance of secondary alkaline zinc electrode, Materials chemistry and
physics 84 (2004) 99106.
[25] D. Yuan, J. Zeng, N. Kristian, Y. Wang, X. Wang, Bi2O3 deposited on highly
ordered mesoporous carbon for supercapacitors, Electrochemistry
Communications 11 (2009) 313317.
[26] D. Cericola, P. Ruch, R. Ktz, P. Novk, A. Wokaun, Characterization of bi-
material electrodes for electrochemical hybrid energy storage devices,
Electrochemistry Communications 12 (2010) 812815.
[27] A.M. Fogg, A.J. Freij, G.M. Parkinson, Synthesis and anion exchange chemistry
of rhombohedral Li/Al layered double hydroxides, Chemistry of materials 14
(2002) 232234.
[28] D. Kubo, K. Tadanaga, A. Hayashi, M. Tatsumisago, Improvement of
electrochemical performance in alkaline fuel cell by hydroxide ion
conducting NiAl layered double hydroxide, Journal of Power Sources 222
(2013) 493497.
[29] J. Tedim, S. Poznyak, A. Kuznetsova, D. Raps, T. Hack, M. Zheludkevich, M.
Ferreira, Enhancement of active corrosion protection via combination of
inhibitor-loaded nanocontainers, ACS applied materials & interfaces 2 (2010)
15281535.
[30] X. Fan, Z. Yang, X. Xie, W. Long, R. Wang, Z. Hou, The electrochemical behaviors
of ZnAlLa-hydrotalcite in ZnNi secondary cells, Journal of Power Sources
241 (2013) 404409.
[31] R. Wang, Z. Yang, B. Yang, T. Wang, Z. Chu, Superior cycle stability and high rate
capability of ZnAlIn-hydrotalcite as negative electrode materials for NiZn
secondary batteries, Journal of Power Sources 251 (2014) 344350.
[32] Z. Feng, Z. Yang, J. Huang, X. Xie, Z. Zhang, Inuences of Zn-Sn-Al-Hydrotalcite
Additive on the Electrochemical Performances of ZnO for Zinc-Nickel
Secondary Cells, Journal of The Electrochemical Society 161 (2014) A1981
A1986.
[33] H. Liu, S. Bi, G. Wen, X. Teng, P. Gao, Z. Ni, Y. Zhu, F. Zhang, Synthesis and
electrochemical performance of Sn-doped Li3V2(PO4)3/C cathode material for
lithium ion battery by microwave solid-state technique, Journal of alloys and
compounds 543 (2012) 99104.
[34] B. Yang, Z. Yang, R. Wang, T. Wang, Layered double hydroxide/carbon
nanotubes composite as a high performance anode material for NiZn
secondary batteries, Electrochimica Acta 111 (2013) 581587.
[35] V. Vivier, A. Regis, G. Sagon, J.Y. Nedelec, L. Yu, C. Cachet-Vivier, Cyclic
voltammetry study of bismuth oxide Bi2O3 powder by means of a cavity
microelectrode coupled with Raman microspectrometry, Electrochimica acta
46 (2001) 907914.
[36] B. Sarma, A.L. Jurovitzki, Y.R. Smith, S.K. Mohanty, M. Misra, Redox-Induced
Enhancement in Interfacial Capacitance of the Titania Nanotube/Bismuth
Oxide Composite Electrode, ACS applied materials & interfaces 5 (2013) 1688
1697.
[37] V. Nithya, R.K. Selvan, L. Vasylechko, C. Sanjeeviraja, Surfactant assisted
sonochemical synthesis of Bi2WO6 nanoparticles and their improved
electrochemical properties for use in pseudocapacitors, RSC Advances 4
(2014) 43434352.
[38] R. Wang, Z. Yang, Synthesis and high cycle performance of ZnAlIn-
hydrotalcite as anode materials for NiZn secondary batteries, RSC Advances 3
(2013) 1992419928.
[39] M.G. Perez, M.J. OKeefe, T. OKeefe, D. Ludlow, Chemical and morphological
analyses of zinc powders for alkaline batteries, J Appl Electrochem 37 (2007)
225231.
[40] J. Jindra, Sealed NiZn cells, 19961998, Journal of power sources 88 (2000)
202205.