DOI: 10.1002/chem.
201703081 Full Paper
& Prussian Blue Cathodes
Role of Acid in Tailoring Prussian Blue as Cathode for
High-Performance Sodium-Ion Battery
Yang Liu,*[a] Gangya Wei,[a] Mengyue Ma,[a, b] and Yun Qiao*[a, b]
Abstract: Prussian blue (PB) with concave centers is synthe-
sized successfully through a hydrothermal method with the
assistance of acid. In this study, the role of the acid is investi-
gated systematically by adjusting the reaction temperature
and time, using different kinds and amounts of acid, and
changing the amount of PVP surfactant added. It is found
that the acid can not only trigger the chemical reaction to
form cubic PB, but also act as an etching reagent to tailor
the morphology. The as-obtained cubic PB with concave
centers demonstrates a superior cycle stability and rate per-
formance, which can achieve a capacity of 107 mA h g@1 at
Introduction
Prussian blue (PB) and its analogues AaM’b[M’’c(CN)6]·x H2O (A:
alkali cations; M: metal ions; PBs), as mixed-valence hexa-
cyanoferrate salts, have been utilized as pigments and also in
medicine as antidotes to radioactive cesium and thallium.[1]
They are promising candidates for wide applications in the
fields of catalysis, biomedicine, magnetism, and energy storage
because of its open framework and special properties with in-
terstitial sites and vacancies, which can intercalate cations and
even some small molecules.[2] However, there are still many
issues and scientific problems with PBs, which need to be fur-
ther investigated and understood.[3] Extensive efforts have
been made to disclose the structure–function relationship of
the composition, crystal water style, and vacancies or intersti-
tial sites in the structure.[4] Takahashi et al. proved the associa-
tion between the adsorption of gaseous ammonia and the
chemical composition of PBs.[5] The magnetic properties of PB
show a rapid response to humidity because of the adsorption
[a] Dr. Y. Liu, G. Wei, M. Ma, Dr. Y. Qiao
School of Chemistry and Chemical Engineering
Henan Normal University, Xinxiang, Henan, 453007 (P.R. China)
E-mail: liuy986@163.com
liuy986@htu.edu.cn
qyvec@htu.edu.cn
[b] M. Ma, Dr. Y. Qiao
National and Local Joint Engineering Laboratory of
Motive Power and Key Materials, Henan Normal University
Xinxiang, Henan, 453007 (P.R. China)
E-mail: qyvec@163.com
Supporting information and the ORCID identification number(s) for the au-
thor(s) of this article can be found under
https://doi.org/10.1002/chem.201703081.
Chem. Eur. J. 2017, 23, 15991 – 15996
0.2 A g@1. The corresponding capacity retention is 74 % after
500 cycles relative to the second cycle. Even at a current
density of 5 A g@1, the specific capacity remains at
82 mA h g@1. Furthermore, the full cell, using PB as the cath-
ode and hard carbon as the anode, exhibits a high capacity
of 70 mA h g@1 at 0.1 A g@1, and can power an LED light suc-
cessfully. This work provides new insights into the role of
acid in tailoring the morphology of PB, and opens a new
avenue toward the design of unique structures to improve
sodium storage.
and desorption of a ligand water molecule on the cobalt ion,
which can switch the magnetic interaction.[6] You et al. report-
ed that PB with a small number of vacancies and a low water
content can enhance the sodium storage performance.[7] In our
previous work, a nanostructured double-ion-incorporated PB
was prepared as a cathode for sodium-ion batteries, and an ex-
cellent performance was demonstrated.[8] Therefore, it is vital
to obtain desirable PBs for various fields.
With the development of renewable energies, low-cost and
reliable electrical energy storage devices are required in the
field of energy conversion and storage.[9] Considering the limit-
ed lithium resources and the high cost of lithium-ion batteries
(LIBs), sodium-ion batteries (SIBs) are a good choice for large-
scale energy storage.[10] Currently, PBs with controllable and
uniform sizes, unique structures, and special morphologies
have aroused great interest, as these characteristics are well
known to have a great effect on their physicochemical proper-
ties and potential applications as cathodes for SIBs.[11] Mesopo-
rous PBs were reported as superior cathodes for SIBs owing to
their porous structure or well-crystallized nanoparticles and
structural robustness.[12] Additionally, monocrystalline PB nano-
frames with high surface-to-volume ratio, good crystallinity,
and 3 D contactable surface showed superb cycling stability.[13]
As we know, the hydrothermal method is a common, facile,
one-step approach to achieving good control over the mor-
phology and structure by regulating the procedural parame-
ters such as reaction temperature and time, pH value, and so
forth.[14] Yamauchi and co-authors adopted the hydrothermal
method to synthesize PB nanomaterials with cubic and hollow
structures.[15] Herein, the etching mechanism was proposed to
allow hydrochloric acid to diffuse into the mesocrystals and
form hollow cavities. Moreover, surface etching has also been
15991 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Full Paper

reported to allow the formation of PB microframes.[16] It is clear

that chemical etching is a powerful method of tailoring the
final morphology of PB. So far, most research has regarded the
acid as the etching agent. However, comprehensive investiga-
tion of the acid function in the chemical reaction and crystal
growth process is necessary.
In this work, we adopted a hydrothermal method to investi-
gate systematically the role of acid in the formation and crystal
growth of PB. The hydrothermal temperature and PVP as the
surfactant are critical parameters determining the features of
the formed PB microcrystals. It is found that the acid functions
not only for the crystal growth at the very start, but also for
tailoring of the morphology. The as-obtained PB nanocubes
with concave centers as cathode materials in SIBs present
good, long-term cycling performance with a stable capacity of
77.8 mA h g@1 after 500 cycles at 0.2 A g@1. Even at 5 A g@1, a
specific capacity of 82 mA h g@1 can be achieved. The full bat- Figure 1. FE-SEM images of a,d) PB-H1, b,e) PB-H2, and c,f) PB-H3. TEM
tery also shows a high capacity of 70 mA h g@1 at 0.1 A g@1. images of g) PB-H1, h) PB-H2, and i) PB-H3.

Results and Discussion
The synthesis of PBs as cathode materials is based on a hydro-
thermal method, using Na4Fe(CN)6 with PVP as surfactant in
the presence of hydrochloric acid (Scheme 1 a). The morpholo-
Scheme 1. Schematic illustration of a) the synthetic procedure for PBs, and
b) the possible formation mechanism of PB microcrystals with various mor-
phologies.
gy of PB can be tailored by adjusting the amount of acid
added, as shown in Scheme 1 b. Cubic PB, cubic PB with con-
cave centers, and spherical-like PB with concave centers can
be obtained controllably. The reaction conditions are adjusted,
and the specific function of the acid will be discussed in detail.
The influence of acid on the morphology is first investigated
with different HCl amounts (1–3 mL). The typical field-emission
scanning electronic microscopy (FE-SEM) images of the as-pre-
pared PB microcubes (PB-H1) show that a size of approximate-
ly 1 mm is obtained if the addition amount of HCl is 1 mL (Fig-
ure 1 a,d). The PB-H2 product maintains the cubic morphology,
but each surface of the cube exhibits a concave center upon
increasing the HCl amount to 2 mL, as shown in Figure 1 b.
The high-magnification FE-SEM image in Figure 1 e shows that
surface of the cubic PB with concave centers is very rough, im-
plying that HCl has an etching effect. Transmission electron mi-
croscopy (TEM) images can provide further insight into the mi-
crostructures of the samples. The TEM image for PB-H1 dem-
onstrates its solid cubic structure, as shown in Figure 1 g. In
contrast, the center and side of PB-H2 are transparent, indicat-
ing that the concave center is distributed homogeneously on
each side (Figure 1 h). In addition, the TEM image shows that
the diameter and depth of these concave centers are around
350 and 100 nm, respectively, which are consistent with the
SEM images. Furthermore, the mesoporous structure can be
observed in PB-H2 (Figure S1 a, Supporting Information). How-
ever, spherical-like particles and small amounts of nanocubic
PB are obtained in PB-H3 with the acid volume increased to
3 mL (Figure 1 c). The average particle size is approximately
900 nm. Note that six concave features partially remain on the
spherical surface of PB-H3, as illustrated in Figure 1 f, which
also shows the particles to have a rough surface. The TEM
image in Figure 1 i further confirms the spherical structure, and
the concave features are at the top/bottom and central sec-
tions of the spherical-like PB-H3. Moreover, the mesoporous
structure is also present in PB-H3, as shown in Figure S1 b
(Supporting Information).
The as-obtained samples were further investigated through
X-ray diffraction (XRD) to evaluate the phase structure, as
shown in Figure 2 a. For these three samples, the peaks at 2q
Figure 2. a) XRD patterns and b) FTIR spectra of PB-HX samples.

Chem. Eur. J. 2017, 23, 15991 – 15996 www.chemeurj.org 15992 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

values of 17.58, 24.88, 35.38, 39.68, 50.78, 54.08 and 57.28 corre-
spond to the (200), (220), (400), (420), (440), (600), and (620)
crystal planes. These peaks can be indexed to the face-cen-
tered cubic structure (JCPDS No. 73–0687), confirming the for-
mation of PB without other impurity phases. The FTIR spectra
of the as-obtained PB products are displayed in Figure 2 b. All
the samples show a distinct absorption peak at 2084 cm@1,
which is ascribed to the characteristic vibration of the @C/N@
group. The weak absorption at around 498 cm@1 indicates the
presence of FeII@CN@FeIII in the samples. Additionally, the weak
absorptions at 1611 and 1414 cm@1 are associated with the
C=O stretching vibration arising from PVP, which suggests that
there is residual PVP in the as-obtained PB products.
On the basis of the morphology, structure, and microstruc-
ture characterizations of the as-obtained PB samples, as illus-
trated above, HCl plays an important role in tailoring the mor-
phology through etching. Note that the cubic morphology is
formed with as low as 1 mL HCl addition. Upon increasing the
addition amount to 2 mL, etching occurs on six faces of the
cubic structure, and the concave cubic structure is obtained.
Upon increasing the acid amount continuously 2 mL to 3 mL,
the etching first appears on the centers of the cubic facets,
then on the corners and edges, because the stability of the
cubic facets is much lower than that of the corners and edges.
A spherical-like structure is obtained, and some parts are par-
tially etched.
For further comprehension of the effect of acid on the mor-
phology and structure of the PB product, control experiments
were designed using H2SO4 and HNO3 instead of HCl. Upon ad-
dition of 1 mL H2SO4 or 1 mL HNO3 with the other conditions
remaining the same, the morphologies of the products are
almost the same as PB-H1, and are composed of a large
number of microcubic structures, as exhibited in Figure S2
(Supporting Information). These results demonstrate that the
acid in the reaction system is a key factor in the tailoring of
PB, and also support the conclusion that PBs with cubic mor-
phology are inclined to be formed with a relatively low acid
amount.
Furthermore, the role of PVP in the reaction process is also
considered. In the absence of PVP, PB with cubic morphology
can also be obtained, but the size distribution is broad, rang-
ing from 1 to 5 mm (Figure S3, Supporting Information). In gen-
eral, PVP as an amphiphilic surfactant can be dissolved in
water and also in organic solvents. Moreover, the metal ions in
solution can be coordinated with the pyrrolidone groups in
PVP.[17] Hence, the pyrrolidone groups are coordinated with
iron ions during the nucleation and growth processes.[18] The
PVP as a protective layer can be formed on the PB surface, so
the size distribution can be adjusted and the etching effect of
acids can be slowed down. The hydrothermal reaction time is
also considered using 2 mL HCl, and the corresponding SEM
images of PB are collected to analyze the morphology evolu-
tion. With a hydrothermal time of 20 min, the cubic and con-
cave cubic morphologies appear in the samples, with an aver-
age particle size of approximately 1 mm. After 120 min, the as-
obtained PB is composed of the cubic structure and sphere-
like morphology with concave areas on the surface (Figure S4,
Chem. Eur. J. 2017, 23, 15991 – 15996 www.chemeurj.org
Full Paper
Supporting Information). These imply that PVP as a surfactant
can control the particle size distribution, and the etching effect
is greater with more acid and a longer reaction time.
The above results demonstrate that the acid amount in the
initial solution and the PVP surfactant have a great effect on
the crystal growth and morphology evolution. There is no
doubt that the acid can etch the sides of the cubes and tailor
the morphology, and that the PVP as surfactant can control
the size distribution. Note that the acid is not only an etching
reagent, but also a catalyst to propel the chemical reaction. At
a certain temperature, Na4Fe(CN)6 will decompose into iron
ions under acidic conditions. These iron ions will react immedi-
ately with Fe(CN)4@6 , generate a PB crystal, and form the micro-
cubic morphology. A series of experiments were conducted to
study the reaction mechanism further. In the absence of HCl,
the product with red–brown color is collected, as shown in
Figure S5 a (Supporting Information). The corresponding XRD
pattern indicates that only Fe2O3 is obtained (Figure S5 b).
Upon performing the reaction at room temperature, only a
small amount of blue precipitate with cubic morphology is ob-
tained after two days, indicating that the hydrolysis rate is very
slow in this situation (Figures S6 and S7, Supporting Informa-
tion). Generally, a blue precipitate can be obtained immediate-
ly upon addition of FeCl2 into Na4Fe(CN)6 aqueous solution at
room temperature through a co-precipitation method, as re-
ported in our previous work.[19] This result further proves the
above analyses. Therefore, the chemical reaction processes can
be described as shown in Equations (1) and (2).
þ
H
2Na4 FeðCNÞ6 KKK! 8Naþ þFe2þ þFeðCNÞ4@
6 þ6CN
@
ð1Þ
Hþ
2Naþ þFe2þ þFeðCNÞ4@ () Na2 FeFeðCNÞ6 # ð2Þ
6
The structures and electrochemical performances of the PB-
HX samples are investigated further. X-ray photoelectron spec-
troscopy (XPS) is used to analyze the chemical composition
and surface electronic state. The survey XPS spectra in Fig-
ure 3 a demonstrate the presence of C, N, O, Fe, and Na in all
three samples. The high-resolution Fe 2p spectra display the
electron binding energies at 708.3 and 721.3 eV, which can be
assigned to FeII 2p3/2 and FeII 2p1/2, and the FeIII 2p3/2 and
FeIII 2p1/2 signals can also be detected at 709.0 and 723.4 eV.
Moreover, the other two peaks at 712.1 and 725.0 eV corre-
spond to FeIII 2p3/2 and FeIII 2p1/2, respectively.[9b] This indicates
that a small amount of FeIII is present in these three samples.
The thermogravimetry and differential scanning calorimetry
(TG/DSC) curves are used to calculate the weight loss, as
shown in Figure S8 (Supporting Information). In the DSC curve,
the endothermic peak at approximately 200 8C is attributed to
the removal of adsorbed and interstitial water in the PB struc-
ture. From the TG curves, weight losses of 12.1 %, 13.1 %, and
16.4 % occur in PB-H1, PB-H2, and PB-H3, respectively. The
water content is increased with more acid etching, owing to
the increase in vacancies or interstitial sites to accommodate
zeolitic water with the dissolution of the PB surface. Inductively
coupled plasma optical emission spectrometry (ICP-OES) is
15993 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 3. a) Survey XPS spectra of PB-HX; b) high-resolution Fe 2p spectra for
PB-HX; c) nitrogen adsorption/desorption isotherms of PB-H2; d) BJH pore
size distribution of PB-H2 from adsorption data.
used to analyze the specific element contents of the PB-HX
samples. The Na/Fe molar ratios of the three samples are
0.916:1, 0.903:1, and 0.311:1, respectively, which indicates that
the etching process can also influence the sodium ions in the
structure. Moreover, the PB-H3 sample presents a low sodium
content, indicating that ion exchange occurs and sodium ions
are replaced by hydrogen ions in the tunnel structure with
3 mL HCl. The surface area and pore size distribution were ana-
lyzed further from nitrogen adsorption/desorption isotherms
and Barrett–Joyner–Halenda (BJH) pore-size distribution plots.
The nitrogen adsorption and desorption isotherms of PB-H2
show the typical type IV isotherms with a distinct H2 hysteresis
loop, and the pore-size distribution plot indicates a mesopo-
rous structure (Figure 3 c and Figure 3 d). PB-H1 shows typical
type II isotherms with an H4 hysteresis loop, and the corre-
sponding pore-size distribution plot proves that no micropores
and mesopores exist in this sample (Figure S9 a,b, Supporting
Information). On the other hand, PB-H3 shows typical type IV
isotherms with a distinct H4 hysteresis loop, and both meso-
pores and micropores coexist in this sample. Moreover, the
BET specific surface area increases from 7.38 m2 g@1 for PB-H1
to 121.40 m2 g@1 for PB-H2, and then up to 228.47 m2 g@1 in PB-
H3. From the above results, it can be deduced that hydrochlo-
ric acid can act as a catalyst to propel the synthesis of PBs
with an addition amount of 1 mL. With an increased acid
amount, it also acts as an etching agent to tailor the morphol-
ogy and adjust the specific surface area accordingly.
The electrochemical performances of the three samples as
cathode materials were evaluated in coin cells with sodium
foils as the counter electrodes. The galvanostatic charge and
discharge behaviors of the PB-HX samples were first measured
at a current density of 0.2 A g@1. The first charge/discharge pro-
files are shown in Figure 4 a; all three electrodes display a pro-
nounced voltage plateau at around 3.1 V and another incon-
spicuous plateau at approximately 3.6 V during the charge pro-
cess. In the discharge process, one sloping plateau and a long
flat voltage plateau at about 3.4 and 2.9 V can be observed,
which also can be assigned to the FeII/FeIII redox reaction ac-
Chem. Eur. J. 2017, 23, 15991 – 15996 www.chemeurj.org
Full Paper
Figure 4. a) The first charge and discharge curves of the PB-HX electrodes;
b) CV curves of the PB-H2 electrode from 2.0 to 4.2 V at a scan rate of
0.2 mV s@1; c) rate performance of PB-HX in the potential range 2.0–4.2 V;
d) cycling performance of PB-HX at a current density of 0.2 A g@1.
companied by the insertion/extraction of sodium ions. The ini-
tial charge/discharge capacities are 92.1/90, 97/107, and 56.4/
81.1 mA h g@1 for PB-H1, PB-H2, and PB-H3 electrodes, respec-
tively. PB-H2 shows the highest charge and discharge capaci-
ties, whereas the PB-H3 electrode displays the poorest per-
formance. The best performance of PB-H2 could be attributed
to two aspects. The first is its unique structure, that is, the
cubic structure with concave areas in each side, which can
shorten the ion and electron diffusion length and provide a
large contact area between the electrode and electrolyte. The
second aspect is the relatively high content of sodium: Na-rich
PB would show a better performance than Na-poor PB, as re-
ported in our previous work.[19]
The electrochemical process of the PB-HX samples as catho-
des was analyzed by cyclic voltammetry (CV). Figure 4 b pres-
ents the CV curves of the PB-H2 electrode from 2.0 to 4.2 V at
a scan rate of 0.2 mV s@1. For the PB-H2 as cathode, two cou-
ples of well-separated redox peaks are located at 3.6/3.4 V and
3.1/2.9 V, which are assigned to the oxidation/reduction of
low-spin and high-spin FeII/FeIII couples binding to N and C
atoms with @C/N@ ligands, respectively. This is in accordance
with the above charge and discharge curves. The almost iden-
tical CV profiles in the subsequent three cycles indicate that
the electrode has high electrochemical stability. The other CV
profiles of the electrodes (Figure S10, Supporting Information)
show similar shapes to that of PB-H2 and exhibit good repro-
ducibility.
Figure 4 c shows the specific charge and discharge capacities
of the three samples as cathodes at different current densities.
After ten cycles, the PB-H2 cathode delivered a reversible ca-
pacity of 93.1 mA h g@1 at a current density of 0.2 A g@1. The re-
versible capacities at 0.5, 1, 2, 3, and 5 A g@1 are 90.8, 89, 88.3,
85.9, and 82 mA h g@1, respectively. The cathode can also ach-
ieve a reversible capacity of 91.6 mA h g@1 upon returning the
current density back to 0.2 A g@1 from 5 A g@1, indicating its ex-
cellent stability at various current densities. Compared with
the PB-H2 cathode, the PB-H1 and PB-H3 electrodes demon-
15994 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

strate relatively low specific capacities, especially at a high
rate. The specific capacities of PB-H1 and PB-H3 are only 72.3
and 68.1 mA h g@1, respectively, at a current density of 5 A g@1.
Therefore, the morphology tailoring in this work provides an
effective route to designing cathodes with high rate perform-
ances.
The cycling performance was evaluated further at a current
density of 0.2 A g@1 in the voltage range 2.0–4.2 V, as illustrated
in Figure 4 d. The PB-H2 electrode definitely exhibits the high-
est specific capacity and the best stability. The specific capacity
decreases gradually to 90.4 mA h g@1 in the 80th cycle from its
initial capacity of 107 mA h g@1, then it stabilizes at about
80 mA h g@1 after 340 cycles. A specific capacity of
77.8 mA h g@1 is retained after 500 cycles; this corresponds to a
capacity retention of 74 % compared with the second cycle, in-
dicating the stable and long-term cycling life of this electrode.
On the contrary, the PB-H3 sample presents a low capacity and
unstable cycling performance. The specific capacity decays to
46.9 mA h g@1 from an initial capacity of 84 mA h g@1 over 500
charge and discharge cycles. We speculate that this inferior
performance can be attributed to its Na-poor state. Because
the amount of added HCl is high, the sodium atoms in the
tunnel structure may be substituted by hydrogen atoms. On
the basis of above analyses, the best electrochemical per-
formance shown by PB-H2 is attributed to the following fac-
tors: 1) the cubic structure with concave centers on each side
is favorable for the transfer of ions and electrons, and hence,
promotes the sodium storage performance, particularly at high
rates; and 2) the Na-rich state is beneficial in terms of decreas-
ing the vacancies or interstitial sites of the cathode and then
stabilizing the structure during the insertion/extraction of
sodium ions.
Full cells were assembled to evaluate the possible applica-
tion of this cathode. Figure 5 a presents a schematic diagram
of the structure of the full cell with PB-H2 as the cathode and
hard carbon as the anode. A light-emitting diode can be pow-
ered successfully by the coin full cell, as shown in Figure 5 b.
Figure 5. a) Schematic structure of the full cell with PB-H2 as the cathode
and hard carbon as the anode; b) optical photograph of a commercial white
light-emitting diode in dim background; c) typical charge and discharge
curves of a PB-based full cell; d) cycle performance of the full cell at a cur-
rent density of 0.1 A g@1.
Chem. Eur. J. 2017, 23, 15991 – 15996 www.chemeurj.org
Full Paper
The typical charge and discharge curves of a PB-based full cell,
shown in Figure 5 c, were obtained at a constant current densi-
ty of 0.1 A g@1 in the range 1.5–3.6 V. A reversible capacity of
67.8 mA h g@1 can be obtained in the first cycle. The charge
and discharge plateaus remain during the cycling process.
Note that the capacity has a tendency to increase up to
70 mA h g@1 after 20 cycles. This implies an exciting possibility
for the application of PB cathodes for future SIBs, which are
promising candidates for large-scale electrochemical energy
storage.
Conclusion
Prussian blue has been synthesized successfully through a hy-
drothermal method, and the morphology tailored by adjusting
the addition amount of acid. The function of the acid was
studied systematically, and it was found that the acid can act
not only as an etching reagent, but also as a catalyst to propel
the chemical reaction. The PB cubic structure with concave
centers as a cathode material for SIBs presents a good cycling
stability and excellent rate performance. This work provides an
opportunity for further exploration of the relationship between
the structure and sodium storage performance, and demon-
strates that PBs have great potential for application as catho-
des for large-scale energy storage systems.
Experimental Section
Synthesis
PVP (4.5 g) was dissolved in double distilled water (60 mL) in a
Teflon vessel. Then, an appropriate amount of hydrogen chloride
acid aqueous solution (6 mol L@1) and Na4Fe(CN)6·10 H2O (0.197 g)
were added sequentially to the above solution. Subsequently, the
vial was transferred into a stainless autoclave and heated at 150 8C
for 1 h in an electric oven. The resulting blue precipitate was cen-
trifuged and washed three times with distilled water and ethanol.
The products were dried in a vacuum oven at 80 8C for 12 h, and
the as-obtained products were denoted PB-HX (X = 1, 2, 3), in
which X represents the volume of HCl aqueous solution (1, 2, and
3 mL, respectively).
Characterizations
The structures of the products were examined by X-ray diffraction
(XRD, D8 Advance, Bruker) using CuKa radiation. The morphology
was determined by field-emission scanning electronic microscopy
(FE-SEM; JSM-6700F). Transmission electron microscopy (TEM)
images were recorded with a JEOL JEM-2100 microscope. X-ray
photoelectron spectroscopy (XPS) was performed on a VG Multi-
Lab 2000 system with a monochromatic AlKa X-ray source. All the
spectra were calibrated with the C 1s peak at 284.6 eV. Thermogra-
vimetric analysis (TGA) and differential scanning calorimetry (DSC)
were conducted on a Netzsch STA449F3 analyzer from 50 to 450 8C
at a rate of 10 8C min@1 in flowing air. The chemical compositions
and molar ratios of Na and Fe were determined by inductively cou-
pled plasma optical emission spectrometry (ICP-OES, Optima
4300DV, USA). The specific surface areas and pore size distributions
were determined by the Brunauer–Emmett–Teller technique (BET,
Micromeritics ASAP 2020 analyzer) and the Barrett–Joyner–Halenda
15995 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

(BJH) method, respectively. FTIR spectra were recorded with a
NEXUS spectrophotometer for powder samples diluted with KBr.
Electrochemical measurements
Electrochemical performances were evaluated with CR2025 coin
half cells. The working electrode slurry was manufactured by
mixing 70 wt % active material, 20 wt % conductive carbon, and
10 wt % sodium alginate, and was coated onto the aluminum foil.
The slurries were dried overnight at 80 8C under vacuum. Coin cells
were assembled in an argon-filled glove box (H2O, O2 < 0.1 ppm).
Glass fiber from Whatman (GF/D) was used as the separator,
sodium metal as the counter electrode, and NaClO4 (1.0 mol L@1) in
a mixed solvent of propylene carbonate (PC) and ethylene carbon-
ate (EC) (1:1, vol/vol) with 5 vol % nonreactive fluoroethylene car-
bonate (FEC) additives as the electrolyte. For the full cell, hard
carbon with super P and carboxymethyl cellulose (8:1:1) were
mixed and coated onto copper foil as the anode electrode. The
anode was first activated for three cycles under a low current den-
sity of 50 mA g@1 in a half cell in the voltage range 0.01–3 V versus
Na/Na + . Then, the as-disassembled electrode was utilized to as-
semble a full cell with PB as the cathode. The charge/discharge
tests were conducted with a CT2001A testing system (LAND Elec-
tronic Co. Ltd) within a voltage window of 2.0–4.2 V. Cyclic voltam-
metry (CV) measurements were performed on a CHI 760B electro-
chemical workstation in the range 2.0–4.2 V at a scan rate of
0.2 mV s@1.
Acknowledgements
This work was supported by the Natural Science Foundation of
China (Grant No. 21503071 and 21501049), and the Fund of
Key Scientific and Technological Project of Henan Province (No.
172102210353).
Conflict of interest
The authors declare no conflict of interest.
Keywords: cathodes · electrochemistry · hydrothermal
synthesis · Prussian blue · sodium-ion batteries
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Manuscript received: July 4, 2017
Accepted manuscript online: September 8, 2017
Version of record online: October 18, 2017
15996 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim