Materials Technology

Advanced Performance Materials

ISSN: 1066-7857 (Print) 1753-5557 (Online) Journal homepage: http://www.tandfonline.com/loi/ymte20

Recent developments on aqueous sodium-ion

batteries

Yang You, Zhongsheng Sang & Jinping Liu

To cite this article: Yang You, Zhongsheng Sang & Jinping Liu (2016) Recent developments
on aqueous sodium-ion batteries, Materials Technology, 31:9, 501-509, DOI:
10.1080/10667857.2016.1189709

To link to this article: http://dx.doi.org/10.1080/10667857.2016.1189709

Published online: 25 Jul 2016.

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 Recent developments on aqueous sodium-ion
batteries
Yang You2‡, Zhongsheng Sang2‡ and Jinping Liu1*

For the extensive utilisation of renewable energy in future, we urgently require new generation of electric
energy storage technologies that are low cost, environmentally friendly and sustainable in terms of
the electrode and electrolyte materials. Therefore, sodium-ion batteries come back into our horizon.
Aqueous sodium-ion batteries exhibit better safety and low cost, providing an excellent prospect for
widespread use. Nevertheless, there are still lots of difficulties in developing sodium-storage electrodes
and aqueous sodium-ion technology. This review will mainly summarise recent developments of
aqueous sodium-ion battery electrodes and the relating electrochemical energy storage reactions.
The advantages/disadvantages of typical electrodes as well as future directions in aqueous sodium-ion
Downloaded by [Simon Fraser University] at 18:34 31 July 2016

storage will also be discussed at the end.

Keywords:  Recent developments, Sodium-ion batteries, Aqueous electrolyte, Electrode materials

This paper is part of a special issue on Hybrid electrode materials for energy storage

Introduction to aqueous sodium-ion on analysing the recent advances in ASIB, especially on the
electrode materials, and make comparison on each kind of
batteries materials. Some future directions in this field will also be
Recently, as a renewable and sustainable energy storage tech- finally presented.
nology, aqueous rechargeable sodium-ion batteries (ASIBs)
have becoming a hotspot due to the environmental friendli-
ness, safety and low cost. Not like traditional lithium-ion bat- Electrodes for ASIBs
teries, ASIBs have many advantages for large-scale stationary To be used in ASIBs, electrode materials should satisfy sev-
electric storage, such as low cost of Na, its abundant resource eral requirements. First of all, as we have discussed in the
compared to Li and the stable electrochemical performance. introduction, the electrode’s redox potentials should locate
In addition, aqueous electrolytes are inherently safer and more between O2 and H2 evolution potentials to avoid water elec-
eco-friendly than organic electrolytes.1 trolysis. Secondly, cathode materials used in ASIBs should
However, difficulties still exist in developing Na-storage contain Na, otherwise we must employ pre-sodiated anode to
technology. Like any other aqueous batteries, ASIBs’ thermo- ensure the presence of Na+ in the system. Thirdly, electrode
dynamic properties are seriously affected by water evolution materials should be chemically stable in specific pH so that
reactions. As shown in Fig. 1, the stable thermodynamic elec- dissolution of electrode will not occur.
trochemical window is ~1.23 V. In order to prevent the side
reactions of hydrogen and oxygen evolutions, the potential
of Na-insertion cathodes should be lower than the oxygen Cathode materials
evolution potential; on the other hand, the potential of anode
Na-insertion reaction should be above the hydrogen evolu- Oxides
tion potential. Therefore, most conventional high-potential Previous studies in aqueous electrochemical energy storage
cathodes and low-potential anodes (e.g. Sn, Sb, P and related systems revealed that transition metal oxides (e.g. MnO2,
alloys) are not suitable for ASIBs. Besides, Na’s ion radius RuO2, V2O5, et al.) show highly reversible charge storage
is larger than Li’s, which makes Na-insertion reaction more properties. These materials were mainly used for superca-
difficult as compared to Li insertion. Furthermore, its large pacitor applications due to the well-known surface Faraday
ion radius even causes the collapse of electrode structure and process. But recently, Ghodbane et al. synthesised a series
then affects the cycling stability.2 of tunnel-structure MnOOM (M represents alkali-metal ions
For all reasons given above, for the ASIB devices there such as Na+)4 and found that the capacitance of some large-
are only few stable electrode systems with good application size tunnelled or layered structure can reach 150–300 F/g.
performance.1−3 To better understand this, our review focuses From further experimental analysis, they figured out the
energy storage mechanism is Na+ insertion/de-insertion rather
1
School of Chemistry, Chemical Engineering and Life Science and than surface effect.
State Key Laboratory of Advanced Technology for Materials Synthesis In 2008, Komaba et al.5 discovered a promising Na storage
and Processing, Wuhan University of Technology, Wuhan, P.R. China
2
Department of Materials Science and Engineering, Wuhan University of capability of ca. 25–30  mAh/g in birnessite-type δ-MnO2,
Technology, Wuhan, P.R. China which has a layered structure and can achieve reversible Na
*Corresponding author, email [email protected] insertion/de-insertion.
‡
These authors contributed equally to the work.

© 2016 Informa UK Limited, trading as Taylor & Francis Group

Received 29 April 2016; accepted 10 May 2016
DOI 10.1080/10667857.2016.1189709 Materials Technology: Advanced Performance Materials   2016  VOL. 31   NO. 9 501
 You et al.  Recent developments on aqueous sodium-ion batteries

1.5 in Fig. 2d shows at least three redox peaks, indicating that

NaMnO2 Na2MFe(CN)6
V2O5
PTVE 4.0 Na-insertion process is a multiphase reaction. The results
1.0
Na0.44MnO2 are identical to those reported by Sauvage et al., who uti-
3.5 lized Na0.44MnO2 as a selective Na-ion sensor.7 According
O2

Potential/V(vs Na /Na)
ev
Potential/V(vs NHE)

0.5
ol
to his work, at least six intermediate phases were confirmed
ut

+
io
3.0
n by potentiostatic intermittent titration technique and in situ
0 XRD analysis. Whereafter, Whiracre et al. synthesised spi-
2.5
nel LiMn2O4 and after delithiation, it became a spinel type
H

-0.5 λ-MnO2.8 Figure 3 displays the galvanostatic discharge curves

2
ev
ol

AC 2.0 of λ-MnO2 and Na0.44MnO2 cycled in a 1 M Na2SO4 aque-

ut

NaTi2(PO4)3
io

PVAQ
n

-1.0 PI
ous electrolyte (AC as counter electrode in both batteries).
1.5 Surprisingly, spinel-type λ-MnO2 gains a high specific capac-
-1.5 ity of about 80 mAh/g. Moreover, its discharge voltage pla-
7 14 pH
teau increases 0.4 V as compared to Na0.44MnO2, and λ-MnO2
//AC cell delivered almost 70% of theoretical capacity at 6 C
1 Electrochemical window of aqueous electrolyte and the
intercalation potential of some electrode materials that without capacity loss up to 5000 cycles (Fig. 3b). Recently,
could be employed for ASIBs. Reprinted with permission Kim et al. used EIS impedance spectroscopy to investigate
from Ref. 2. Copyright 2013 Journal of Inorganic Materials Na+ diffusion process in Na0.44MnO2,9 and the ion diffusivity
was determined to be 1.08 × 10−13–9.15 × 10−12 cm2/S, which
is much higher than in non-aqueous electrolyte. The above
Whitacre et al. reported another promising cathode for data suggest that Na-insertion reaction can also realise high-
ASIBs, that is, Na0.44MnO2.6 They reported an asymmetric rate charge/discharge in aqueous electrolytes.
hybrid electrochemical capacitor composed of an inser- Zhang et al. reported the electrochemical activity of
Downloaded by [Simon Fraser University] at 18:34 31 July 2016

tion-based Na0.44MnO2 cathode and an activated carbon (AC) Na-containing birnessite-type NaxMnO2 in aqueous elec-
anode that stored charges on surface through capacitive reac- trolyte.10 They firstly synthesised rod-like Na0.95MnO2 and
tion. A specific capacity of ca. 45 mAh/g was obtained at C/8 then used zinc anode to construct a full cell. Figures 4a–b
rate, and 20 mAh/g of the capacity was maintained when the illustrates the galvanostatic charge/discharge curves at dif-
rate was increased up to 18 C (Figs. 2a–b). Figure 2c shows ferent C rates and the cycle stability at 4 C rate. Reversible
that the Na0.44MnO2 cathode can hold 1000 cycles without capacities of 60 and 12 mAh/g are obtained at 2 and 15 C rate,
capacity loss at 4 C. In addition, its cyclic voltammetric curve respectively. The cycling performance is very good with only

2 
a Low-rate discharge curve of a Na0.44MnO2/activated carbon full cell. b Discharge curves at different C rates. c Cycle
performance at 4 C rate. d CV collected from a three-electrode cell with Na0.44MnO2 as working electrode in 1 M Na2SO4, vs.
Hg/HgSO4 reference electrode. Reprinted with permission from Ref. 6. Copyright 2010 Elsevier

502 Materials Technology: Advanced Performance Materials   2016  VOL. 31   NO. 9

 You et al.  Recent developments on aqueous sodium-ion batteries

a Galvanostatic discharge curves of Na0.44MnO2 and λ-MnO2 cycled in 1 M Na2SO4 aqueous electrolyte. b Cycle life test at
3 
6 C rate. Reprinted with permission from Ref. 8. Copyright 2012 Elsevier
Downloaded by [Simon Fraser University] at 18:34 31 July 2016

4 
a Charge and discharge curves of the rod-like Na0.95MnO2 at different rates using Zn metal as the counter electrode.
b Cycling performance of the Zn//Na0.95MnO2 ASIB at 4 C rate with a fixed full charge capacity of 40  mAh/g based on
Na0.95MnO2. c Charge/discharge curves of Na0.35MnO2//Zn and Na0.95MnO2//Zn cells at 200 mA/g. d Cycle performance of the
Na0.35MnO2//Zn cell at 200 mA/g. Reprinted with permission from Ref. 11. Copyright 2014 Elsevier

8% capacity loss after 1000 cycles at 4 C. Later this group transformation will occur, which results in 24% capacity
compared Na0.35MnO2 and Na0.95MnO2, and claimed that decay after only 25 cycles. So, it is highly necessary to restrict
Na0.35MnO2 performs better than Na0.95MnO2 (Figs. 4c–d).11 the structure variation of γ-MnO2 by surface modification for
Na0.35MnO2 was found to deliver higher reversible capacity practical applications.
(43.6 mAh/g) at ca. 200 mA/g and can be cycled continuously
and stably up to 5000 cycles. Prussian blue analogues
Minakshi et al. reported γ-MnO2 as the cathode for
ASIBs.12 Even its specific capacity is approaching 225 mAh/g, Not like Li+ insertion, Na+ insertion/de-insertion is more dif-
but during the electrochemical reaction, a severe structure ficult because of its large ionic radius. In addition, Na+ is

 Materials Technology: Advanced Performance Materials  2016  VOL. 31   NO. 9 503

 You et al.  Recent developments on aqueous sodium-ion batteries

6 Cycle performance and charge/discharge profiles of the

10th and 1000th cycles of maricite in 2 M NaOH. Reprinted
from Ref. 19. Copyright 2013 American Chemical Society

Due to the unique open structure, Prussian blue ana-

logues have shown distinguished Na insertion/de-insertion
Downloaded by [Simon Fraser University] at 18:34 31 July 2016

rate. Regretfully, neither NiCHF nor CuHCF can be paired

with Na-free anodes because they are sodium-depleted state.
Hence, Wu et al. recently reported sodiated Prussian blue
analogues of Na2NiHCF and Na2CuHCF.17,18 Compared with
5 The unit cell of the Prussian Blue crystal structure with sodium-depleted Prussian blue analogues, a reversible capac-
open framwork. Reprinted with permission from Ref. 16. ity of 65 mAh/g was still obtainable at a redox potential of
Copyright 2011 American Chemical Society 0.4–0.6 V, without significant capacity decay at high C rate,
and the sodiated Prussian blue analogues also demonstrate
stable cycle performance up to ca. 500 cycles.
relatively stable in oxide lattice, resulting in structure transi-
tion during Na insertion/de-insertion.
To solve these problems, the researchers tried to use Polyanionic compounds
non-oxide lattices as the Na-storage materials. An open
framework crystal structures is important in this regard. Minakshi et al. firstly used polymer-assisted sol–gel technique
Prussian blue analogues have archetypal hexacyanometalate to produce maricite NaCo1/3Ni1/3Mn1/3PO4 and demonstrated
framework structures and can be described using the general its electrochemical activity in aqueous electrolyte.19 They
formula AxPR(CN)6, in which nitrogen-coordinated transi- found that reversible Na insertion/de-insertion is possible in
tion-metal cations (P) and hexacyanometalate complexes the structure of marictie. Figure 6 shows the cycle stability
(R(CN)6) form a face-centred cubic framework with large and galvanostatic charge/discharge curves of the 10th and
interstitial A sites (Fig. 5). This kind of structure provides 1000th cycle of marictie electrode in 2 M NaOH with AC
great convenience for reversible Na insertion. In previous as the counter electrode. From Fig. 6, one can clearly find a
reports,13–15 thin-film NiHCF was found to exhibit good elec- capacitance of ca. 45 F/g, without significant capacity loss
trochemical activity in various aqueous electrolytes through up to 1000 cycles.
the reaction NaNiFeIII(CN)6 + Na+ + e− → Na2NiFeII(CN)6. A Recently, Jung et al. investigated an iron-based pyrophos-
reversible redox reaction with Na at about 0.3 V (vs. SCE) phate compound Na2FeP2O7 as a cathode for ASIBs.20 Figure
can be observed. On the basis of these works, Wessells et 7a shows the galvanostatic discharge profiles of Na2FeP2O7
al. recently synthesised NiCHF and CuHCF using spontane- electrode at 1 C and 5 C in nonaqueous and aqueous electro-
ous precipitation method.16 They proposed that NiCHF and lytes, respectively. From the profiles we can conclude that in
CuHCF can be used as cathode in ASIBs for grid-scale energy aqueous system there is no significant reduction in capacity
storage devices. between 5 C and 1 C. However, a severe decay in capacity was
The formula of NiHCF can be described as observed in nonaqueous electrolytes. Cycle performance of
K0.6Ni1.2Fe(CN)6·3.6H2O. Even though NiHCF’s theoretical over 300 cycles can be achieved for the Na2FeP2O7 electrode
capacity can reach 85 mAh/g and the cycle stability is good, in aqueous electrolyte. (Fig. 7b)
it still has one disadvantage: the redox potential of 0.59 V Song et al. recently reported a promising material,
vs SHE is relatively low for ASIB’s cathode. To solve this NASICON-type carbon-coated Na3V2(PO4)3, as the cathode
problem, Wessells et al. used CuHCF to replace NiCHF and of ASIBs,21,22 and investigated the electrochemical activity
did the same electrochemical tests. The formula of CuHCF in several aqueous electrolytes of 1M Na2SO4, Li2SO4 and
can be described as K0.71Cu[Fe(CN)6]0.72·3.7H2O. For CuHCF, K2SO4. They gained the best performance in Na2SO4 electro-
a much higher redox potential of 1.0 V vs. SHE and a spe- lyte with 209 F/g capacitance (~50 mAh/g of capacity) at 8.5
cific capacity of ~60 mAh/g were obtained. The above results C and 136 F/g (~35 mAh/g) at 42.7 C(Fig. 8a). The different
clearly imply that with different coordination metal, Prussian C rate curves imply that the Na insertion/de-insertion into/
blue analogues can show distinct redox potential. We can from Na3V2(PO4)3 is diffusion-controlled in aqueous electro-
therefore manipulate the cathode redox potential by changing lyte. The cycle performance up to 30 cycles at 8.5 C was
the coordination metal. achieved, as shown in Fig. 8b. Qin et al. recently reported

504 Materials Technology: Advanced Performance Materials   2016  VOL. 31   NO. 9

 You et al.  Recent developments on aqueous sodium-ion batteries

7 
a Charge/discharge profiles of Na2FeP2O7 in 1 M Na2SO4 aqueous electrolyte and 1 M NaClO4 organic electrolyte. b Cycle
performance of Na2FeP2O7 at 1 C and 10 C rates in 1 M Na2SO4 aqueous electrolyte. Reprinted with permission from Ref.
20. Copyright 2014 The Royal Society of Chemistry
Downloaded by [Simon Fraser University] at 18:34 31 July 2016

8 
a Galvanostatic charge/discharge curves of Na3V2(PO4)3 in 1  M Na2SO4. b Cycle performance of Na3V2(PO4)3 at 8.5 C.
Reprinted with permission from Ref. 21. Copyright 2014 Wiley-VCH. c Charge/discharge curves in the first cycle and d
Cycling profiles of NaVPO4F. Reprinted with permission from Ref. 23. Copyright 2014 Elsevier

that NASICON-type NaVPO4F cathode can deliver an initial evolution, which makes it difficult to choose anode materials.
discharge capacity of 54 mA h/g in 5M NaNO3 solution, with There are few materials that can be considered.
two voltage plateaus at 0.2 V and 0.8 V vs. SCE. However,
about 30% capacity decay was observed after only 20 cycles
(Figs. 8c–d).23 NASICON-Type NaTi2(PO4)3
Among several anodes for ASIBs, NaTi2(PO4)3 is the most
promising one. Delmas et al. firstly reported the NASICON-
Anode materials
Type NaTi2(PO4)3 as electrode in nonaqueous electrolytes.24
When used as anode for ASIB systems, the redox potential Two Na ions reversibly insertion/de-insertion in the three-di-
for electrochemical energy storage should be above the H2 mensional structure of NaTi2(PO4)3 and Na3Ti2(PO4)3 can be

 Materials Technology: Advanced Performance Materials  2016  VOL. 31   NO. 9 505

 You et al.  Recent developments on aqueous sodium-ion batteries

Carbon coating is generally required to enhance the electro-

chemical performance.
Wu et al. recently synthesised carbon-coated NaTi2(PO4)3
by microwave synthesis.26 They tried to enhance the elec-
trical conductivity via carbon coating. After optimisation,
the best electrode sample can achieve ~64% of theoretical
capacity (85 mAh/g) at the current density of 15.7 mA/g up
to 20 cycles. Then this group synthesised a graphite-coated
NaTi2(PO4)3 using an additional 15 wt% concentration of
CNTs. This method turns out to be more feasible. They gained
an enormously enhanced specific capacity (98% of the the-
oretical capacity; 130 mAh/g) at the rate of 0.1 C.27 Figure
10a illustrates the galvanostatic charge/discharge curves of
the graphite-coated NaTi2(PO4)3 with Na0.44MnO2 as counter
electrode in aqueous electrolyte. At higher rates like 2 C,
about 44% of the theoretical capacity was decay. Figure 10b
shows that NaTi2(PO4)3/graphite(G)+CNTs exhibits relatively
good cyclability at 1 C with 86% capacity retention up to
100 cycles.

9 
Galvanostatic charge/discharge curves of the Oxides
NaTi2(PO4)3//Na cell in 1 M NaClO4 in ethylene carbonate
Downloaded by [Simon Fraser University] at 18:34 31 July 2016

(EC)/dimethyl carbonate (DMC) (1:1) electrolyte and the

Qu et al. reported the electrochemical behaviour of
NaTi2(PO4)3//Zn cell in 2 M Na2SO4 electrolyte at a current V2O5·0.6H2O nanoribbons in Na-based aqueous electrolytes.28
rate of 2.0  mA  cm−2. Reprinted with permission from Figure 11a demonstrates the galvanostatic charge/discharge
Ref. 25. Copyright 2011 The Electrochemical Society profiles in different aqueous electrolytes. The curve in 0.5 M
Na2SO4 shows a reversible capacity of 43 mAh/g, demonstrat-
ing a linear relationship with time. Nevertheless, the cycling
observed. Later, Park et al. for the first time used NaTi2(PO4)3 performance of V2O5·0.6H2O anode is relatively bad, and the
as anode for ASIBs.25 From Fig. 9, we can see the galvanos- probable reason is the dissolution of Vn+ into the electrolyte.
tatic charge/discharge curves of NaTi2(PO4)3 electrode in both Deng et al. recently used one-dimensional (1D) nanos-
nonaqueous and aqueous electrolytes at 2.0 mA cm−2. Ninety tructured sodium vanadium oxide, Na2V6O16·nH2O, as anode
per cent of the theoretical capacity with two Na insertions material in ASIB.29 The structure of Na2V6O16·nH2O can be
(133 mAh/g) can be achieved in both system. One can also see described as a layered structure with a monoclinic (P2/m)
a redox potential at 2.1 V vs. Na+/Na, characteristic of its two- crystal system. From Fig. 11b, an initial specific capacity of
phase reaction. It is vital that the overpotential phenomenon 123 mAh/g with redox potential at −0.4 V vs. SCE can be
during charge/discharge process was considerably smaller in detected. But its initial charge capacity is merely 42 mAh/g,
the aqueous system than in the nonaqueous system, implying and the capacity fades rapidly in few cycles. To explore the
the advantage of aqueous electrolyte in power capability and reason of the capacity fade, this group utilized ex-situ XRD
energy efficiency. However, the low electrical conductivity of analyses method and figured out the correlation of capacity
NaTi2(PO4)3 impedes the development of this anode material. fading to the irreversible phase transition during Na insertion.

10 
a Charge/discharge profiles of the NaTi2(PO4)3/G−CNT//Na0.44MnO2 cell at various C rates in aqueous electrolyte. b Cycle
properties at 1 C rate. Reprinted with permission from Ref. 27. Copyright 2014 The Electrochemical Society

506 Materials Technology: Advanced Performance Materials   2016  VOL. 31   NO. 9

 You et al.  Recent developments on aqueous sodium-ion batteries

11 
a Galvanostatic charge/discharge curves of V2O5·0.6H2O in 0.5 M different aqueous electrolytes at 100 mA/g. b CV profiles
at different scan rates from 0.5 to 15 mV/s. Reprinted with permission from Ref. 29. Copyright 2014 Elsevier

Organic compounds
To overcome the performance limitations of inorganic anode
materials, many groups have turned their research interest to
organic materials. Qin et al. introduced NTCDA-derived pol-
Downloaded by [Simon Fraser University] at 18:34 31 July 2016

ymide as anode material for ASIB.30 As shown in Figs. 12a–b,

a pair of obvious redox peaks at −0.40/−0.55 V vs. SCE can
be obtained, similar to the redox potentials observed in Li+
aqueous batteries. The charge/discharge capacities are ~184
and 166.5 mAh/g at a current density of 50 mA/g, respec-
tively. In addition, about 83% of the initial capacity can be
retained after 20 cycles.
Choi et al. recently reported the use of poly (2-vinylan-
thraquinone) (i.e. PVAQ) as anode for ASIBs.31 They have
confirmed that during the redox reaction, two Na+ ions are
inserted into the polymer segments. A reversible capacity of
217 mAh/g can be obtained, and only 9% capacity decay was
found after charging/discharging up to 300 cycles (Fig. 12c).

Prussian blue analogues

Pasta et al. recently introduced manganese hexacyanoman-
ganate as the anode for ASIBs.32 This kind of material can be
described as MnII–N≡C–MnIII, and the detailed composition is
K0.11Mn[Mn(CN)6]0.83·3.64H2O. They utilized a precipitation
method to synthesise such material and gained a redox poten-
tial of 0.052 V vs SHE for electrochemical energy storage
with a specific capacity of 57 mAh/g. Galvanostatic cycling
at 1, 5 and 10 C revealed a low potential hysteresis that leads
to high-rate capability (Fig. 13a). In addition, the cycling
stability of MnII–N≡C–MnIII//CuII–N≡C–FeIII full cell in 10 M
NaClO4 reveals a negligible capacity loss up to 1000 cycles
at 10 C rate (Fig. 13b)

Outlook and perspectives

ASIBs are rising as a promising energy storage system for
intermittent/clean and sustainable energy and large-scale
energy utilization. Its low cost, environmentally benign,
safety and abundant resource reserve make it possible to
replace conventional rechargeable batteries for large-scale
applications. However, there are still some tough problems
12 
a CV curves of polymide and NaVPO4F in 5  M NaNO3
required further long-term research before ASIBs can be
solution at 0.1 mV/s. b Cyclability at 50 mA/g in 5 M NaNO3
aqueous solution. Reprinted with permission from Ref. 30. considered for practical applications. For example, due to
Copyright 2011 Elsevier. c Cycle performance of PVAQ in the narrow electrochemical window of water, the available
30 wt% NaOH electrolyte (pH  14) at current density of ASIB electrode materials are rare and need further explora-
5 A/g. Reprinted with permission from Ref. 31. Copyright tion. Structure transformation during Na+ intercalation may
2011 American Chemical Society

 Materials Technology: Advanced Performance Materials  2016  VOL. 31   NO. 9 507

 You et al.  Recent developments on aqueous sodium-ion batteries

13 
a Charge/discharge profiles of MnII–N≡C–MnIII at different C rates. b Cycle performance of MnII–N≡C–MnIII//CuII–N≡C–FeIII
cell at 10 C rate in 10 M NaClO4. Reprinted with permission from Ref. 32. Copyright 2014 Nature Publishing Group

influence the cycle stability and some protection strategies electrolyte, a dense solid electrolyte interphase was formed
should be proposed. The composition and properties of on the anode and the electrochemical activity of water was
aqueous electrolyte have great impact on the performance of reduced, leading to wider electrochemical stability window
Downloaded by [Simon Fraser University] at 18:34 31 July 2016

electrodes and devices, which also needs detailed studies for (2.1 V) and high energy density of 100 Wh/kg. This work pro-
understanding the mechanisms and optimising the electrolyte vides the possibility to reduce water decomposition in ASIBs.
chemistry. Next, we will summarise the advantages and dis- On the whole, ASIBs provide a potential solution to the
advantages of some typical materials below. safe, low-cost and large-scale sustainable energy utilization.
In this review, we have enumerated polyanionic com- It is believed that with more and more electrode materials
pounds, oxides, organic compounds, Prussian Blue analogues discovered and evaluated, the comprehensive performance of
and so on. Among the cathode materials, Na0.44MnO2 is the ASIBs will be improved constantly. In this regard, numerous
most promising and has been widely investigated due to its efforts are still required to achieve breakthroughs in advanced
high chemical stability and low cost. Without any coating it electrode materials and device configurations.
can cycle stably up to amazing 4000 cycles. Nevertheless,
the sloping charge/discharge profiles of Na0.44MnO2 affect
the utilization of Na+. We can only obtain a specific capac- Funding
ity of 45 mAh/g in aqueous electrolyte. To overcome this This work was supported by the National Natural Science
problem, researchers developed many alternatives like MnO2 Foundation of China [grant numbers 51102105, 11104088];
polymorphs for Na0.44MnO2. Then λ-MnO2 come into our the Science Fund for Distinguished Young Scholars of Hubei
horizon. This material demonstrated a relatively high spe- Province [grant number 2013CFA023]; the Youth Chenguang
cific capacity of ~80 mAh/g with the cycle stability up to Project of Science and Technology of Wuhan City [grant
5000 cycles. However, λ-MnO2 was in general fabricated number 2014070404010206]; the Research Start-Up Fund
from LiMn2O4, making the process indirect and inconvenient. from Wuhan University of Technology; and the Fundamental
Then non-oxide lattice for Na+ storage – Prussian Blue ana- Research Funds for the Central Universities [grant number
logues were employed. Prussian blue analogues have unique WUT:2016IVA083].
open framework that allows facile Na diffusion in the struc-
ture, resulting in a high capacity and good cyclability. But
Prussian blue analogues were always operated in electrolytes References
with pH <2, which has influence on the capacity and needs
  1. W. H. Zuo, P. Xu, Y. Y. Li and J. P. Liu: ‘Direct growth of bismuth Film
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On the other hand, NASICON-type NaTi2(PO4)3 is the electrolytes’, Nanomaterials, 2015, 5, 1756–1765.
most typical anode material for ASIBs. It shows a high spe-   2. H.-X. Yang and J.-F. Qian: ‘Recent development of aqueous sodium ion
cific capacity of ~133 mAh/g with potential plateau around batteries and their key materials’, J. Inorg. Mater., 2013, 28, 1165–1171.
  3. M. D. Slater, D. Kim, E. Lee and C. S. Johnson: ‘Sodium-ion batteries’,
−0.6 V vs. SHE. But it is noteworthy that its low average
Adv. Funct. Mater., 2013, 23, 947–958.
potential allowed H2 evolution during the reaction. As a result,   4. O. Ghodbane, J.-L. Pascal and F. Favier: ‘Microstructural effects on charge-
the cycle stability is not good. In addition, NaTi2(PO4)3 has storage properties in MnO2-based electrochemical supercapacitors’, ACS
low electronic conductivity, which requires modification such Appl. Mater. Interfaces, 2009, 1, 1130–1139.
as carbon coating to get steady electrochemical performance.  5. S. Komaba, A. Ogata and T. Tsuchikawa: ‘Enhanced supercapacitive
behaviors of birnessite’, Electrochem. Commun., 2008, 10, 1435–1437.
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