Northumbria Research Link

Citation: Jiang, Yinzhu, Hu, Meijuan, Zhang, Dan, Yuan, Tianzhi, Sun, Wenping, Xu, Ben
and Yan, Mi (2014) Transition metal oxides for high performance sodium ion battery
anodes. Nano Energy, 5. pp. 60-66. ISSN 2211-2855

Published by: Elsevier

URL: http://dx.doi.org/10.1016/j.nanoen.2014.02.002
<http://dx.doi.org/10.1016/j.nanoen.2014.02.002>

This version was downloaded from Northumbria Research Link:

https://nrl.northumbria.ac.uk/id/eprint/15548/

Northumbria University has developed Northumbria Research Link (NRL) to enable users
to access the University’s research output. Copyright © and moral rights for items on
NRL are retained by the individual author(s) and/or other copyright owners. Single copies
of full items can be reproduced, displayed or performed, and given to third parties in any
format or medium for personal research or study, educational, or not-for-profit purposes
without prior permission or charge, provided the authors, title and full bibliographic
details are given, as well as a hyperlink and/or URL to the original metadata page. The
content must not be changed in any way. Full items must not be sold commercially in any
format or medium without formal permission of the copyright holder. The full policy is
available online: http://nrl.northumbria.ac.uk/policies.html

This document may differ from the final, published version of the research and has been
made available online in accordance with publisher policies. To read and/or cite from the
published version of the research, please visit the publisher’s website (a subscription
may be required.)
Author's Accepted Manuscript

Transition metal oxides for high performance

sodium ion battery anodes
Yinzhu Jiang, Meijuan Hu, Dan Zhang, Tianzhi
Yuan, Wenping Sun, Ben Xu, Mi Yan

www.elsevier.com/nanoenergy

PII: S2211-2855(14)00010-X
DOI: http://dx.doi.org/10.1016/j.nanoen.2014.02.002
Reference: NANOEN324

To appear in: Nano Energy

Received date: 10 December 2013

Revised date: 31 January 2014
Accepted date: 4 February 2014

Cite this article as: Yinzhu Jiang, Meijuan Hu, Dan Zhang, Tianzhi Yuan, Wenping
Sun, Ben Xu, Mi Yan, Transition metal oxides for high performance sodium ion
battery anodes, Nano Energy, http://dx.doi.org/10.1016/j.nanoen.2014.02.002

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting
galley proof before it is published in its final citable form. Please note that during
the production process errors may be discovered which could affect the content,
and all legal disclaimers that apply to the journal pertain.
 Transition metal oxides for high performance sodium ion
battery anodes
Yinzhu Jiang a,*, Meijuan Hu a, Dan Zhang a, Tianzhi Yuan a, Wenping Sun b, Ben Xu c, Mi Yan a,*

a
State Key Laboratory of Silicon Materials, Key Laboratory of Advanced Materials

and Applications for Batteries of Zhejiang Province, Department of Materials Science

and Engineering, Zhejiang University, Hangzhou 310027, China

b
CAS Key Laboratory of Materials for Energy Conversion, Department of Materials

Science and Engineering, University of Science and Technology of China, Hefei,

230026, China,

c
Laboratory of Smart Materials and Surface, Mechanical Engineering, Faculty of

Engineering and Environment, Northumbria University, Newcastle, NE1 8st, UK

*Correspondence authors: yzjiang@zju.edu.cn (Y.Z. Jiang); mse_yanmi@zju.edu.cn

(M. Yan)

Abstract

Sodium-ion batteries (SIBs) are attracting considerable attention with expectation

of replacing lithium-ion batteries (LIBs) in large-scale energy storage systems (ESSs).

To explore high performance anode materials for SIBs is highly desired subject to the

current anode research mainly limited to carbonaceous materials. In this study, a

series of transition metal oxides (TMOs) is successfully demonstrated as anodes for

1 / 19
SIBs for the first time. The sodium uptake/extract is confirmed in the way of reversible

conversion reaction. The pseudocapacitance-type behavior is also observed in the

contribution of sodium capacity. For Fe2O3anode, a reversible capacity of 386 mAh

g-1at 100 mA g-1 is achieved over 200 cycles; as high as 233 mAhg-1is sustained even

cycling at a large current-density of 5 A g-1.

Keywords: Sodium ion battery; Anode; Transition metal oxide; Conversion reaction.

1. Introduction

Renewable clean energy technologies are important to address global concerns

regarding depletion of fossil-based resources, global warming and environmental

pollution. However, the widespread implementation of the renewable energy is

seriously hampered by the intermittent nature of geographic and climatic environment.

Energy storage plays a crucial role in succeeding for renewable energy integration

[1-5]. Among the various available energy storage technologies, lithium-ion batteries

(LIBs), being used as power sources of portable electronics for decades, are currently

considered as the dominant candidate to power the next generation of electric vehicles

and stationary applications. Unfortunately, the large-scale commercial manufacturing

of LIBs faces severe challenges from the increasing cost of lithium and the limited

size of reserves (0.006 wt% abundance on earth) [6,7]. On the other hand, there is no

doubt that the sodium resources are inexhaustible and unlimited everywhere around

the world (4th most abundant element, 2.64 wt% on earth). Similar to LIBs,

sodium-ion batteries (SIBs) could provide an alternative chemistry and might thus

2 / 19
become economically more competitive especially in large-scale energy storage

systems (ESSs) [8-11]. Most SIB research were focused on exploration of stable and

low-cost cathode materials, including Prussian blue, NaFePO4 and NaNi0.5Mn0.5O2

[12-14]. There are continuous efforts on exploring the anode material, most of which,

limited in nongraphitic carbonaceous materials. Hard carbon is the top ranked

nongraphitic carbonaceous materials for sodium storage due to the large interlayer

distance and the disorder structure [8]. Stevens and Dahn reported an initial reversible

capacity of hard carbon as high as 300 mAh g-1 [15]. However, some disadvantages

are revealed for non-graphitic carbonaceous materials such as the large irreversible

capacity and poor capacity retention [14-17]. Some approaches on Na-alloying metals

such as Sn and Sb based materials were also confirmed with sodium storage

capability [18-23]. The SnSb/C nanocomposites exhibited 435 mAh g-1 at 100 mA g-1

after 50 cycles; also, a capacity of 274 mAh g-1 was sustained when applying a large

current density of 1000 mA g-1 [19]. Monconduit et al. reported a good cycling

performance of bulk Sb (600 mAh g-1 at C/2 after 100 cycles) subject to the

amorphous intermediate phase NaxSb acting as a buffer to relieve strain [20].

The conversion-type materials (eg. transition metal oxides, TMO), with superior

lithium storage properties, are also proposed to act as anodes for SIBs. The concept

was first demonstrated with the spinel NiCo2O4 which delivered ~200 mAh g-1of

reversible capacity after an initial discharge of 618 mAh g-1 [24]. Balaya et al.

investigated the sodium storage of Fe3O4 anode, which exhibited an initial discharge

of 643 mAh g-1 but accompanied with nearly 50% irreversible capacity and very poor

3 / 19
capacity retention [25]. Recently, α-MoO3 was demonstrated with highly

electrochemical activity for sodium storage, delivering high first cycle sodiation and

desodiation capacities of 771 and 410 mAh g-1 respectively. Moreover, the α-MoO3

anodes showed favorable rate performance 100 mAh g-1 at a current density of 1.117

A g-1 and long durability over 500 cycles [26]. K. Edstr m et. al examined

nanostructured Fe2O3 for both lithium and sodium storage. A specific sodium capacity

of 250 mAh g-1 at 130 mA g-1 was attained after 60 cycles [27]. However, there are

also contradictory reports that transition metal oxides such as FeO, CoO and NiO

showed almost no electrochemical activity with Na-ion [18,28,29]. In all, there are

limited investigation on using TMOs SIB anode and the mechanism remains poorly

understood.

In this paper, we develop a series of TMOs including Fe2O3, NiO, Co3O4 and

Mn3O4 thin films as anodes of SIBs. The results show high electrochemical activities

of all these TMOs in SIBs. Especially for Fe2O3, as high as 386 mAh g-1capacity at

100 mAg-1could be sustained after 200 cycles. More surprisingly, a reversible

capacity of 233 mAh g-1 is achieved even at an ultra-large current density of 5,000

mA g-1, which is one of the best rate performances among all SIB anodes ever

reported. Further investigation clearly indicates that both the traditional conversion

reactions and the pseudocapacitance-type behavior contribute the distinguished

sodium storage performance. This work demonstrates that TMO based materialsmay

actas a suitable candidateforward to develop high performance anodes of SIBs.

4 / 19
2. Experimental section

Preparation of transition metal oxide film: With a precursor solution of 0.005 M

ferric nitrate in ethanol and ethylene glycol (4:1 in volume), porous Fe2O3 thin films

were prepared by electrostatic spray deposition (ESD) technique for 3h on a stainless

steel substrate heated at 180°C (feeding rate:2 mL h-1). The distance and the applied

voltage between the nozzle and substrate were 4 cm and 15kV, respectively. The mass

of the deposited material was measured using a microbalance with an accuracy of

0.002mg (Sartorius CPA26P, Germany) before and after deposition. The deposition

conditions of NiO, Co3O4 and Mn3O4 thin films are listed in Table S1, the other

unlisted conditions remained same as Fe2O3.

Characterization: The crystal structure of the film was characterized with a Rigaku

D/max 2550PC X-ray diffractometer (XRD). The morphology of the film was

observed using scanning electron microscopy (SEM; Hitachi S-4800, Tokyo, Japan).

The crystal structure details were further characterized by transmission electron

microscopy (TEM; CM-200 microscope, PHILIPS, Amsterdam, the Netherlands).

X-ray photoelectron spectroscopic (XPS) measurements were performed with an

ESCALAB 250 X-ray photoelectron spectrometer, using excitation energy of 1486.6

eV (Al Kα).

Electrochemical Measurements: The electrochemical behavior was examined in

CR2025 coin-type cells using the as-deposited films on stainless steel substrate as the

working electrode and sodium foil as the counter and reference electrode, respectively.

Cell assembling was carried out in an argon filled glovebox, in which the oxygen

5 / 19
concentration and moisture level were maintained less than 1 ppm. Celgard 2300

microporous polypropylene was used as a separator. The electrolyte was 1 M NaPF6

in a mixture solvent of ethylene carbonate (EC), diethyl carbonate (DEC) and

propylene carbonate (PC) (4:4:2 by volume). The cells were charged and discharged

galvanostatically on a Neware BTS battery cycler at 0.005-3.0 V (vs Na/Na+). Cyclic

voltammetry (CV) tests were conducted on a CHI660C electrochemistry workstation

between 0.005 and 3.0 V (vs Na/Na+) at 0.1 mV s-1. All the electrochemical

measurements were carried out at room temperature.

3. Results and discussion

Four transitional metal oxide films prepared by ESD technique were identified as

crystalline for Co3O4, Mn3O4 and amorphous for Fe2O3 and NiO by the XRD analysis

(Figure S1). XPS results of the as-prepared samples verify the valence state of the

transition metals (Figure S2). The morphology and cycling performance of Fe2O3,

NiO, Co3O4 and Mn3O4 thin films are shown in Figure 1. The amorphous Fe2O3 film

deposited at 180 °C shows a porous 3D reticular structure with ~500 nm-thickness

grids cross-linked together (Figure 1a). Such a reticular architecture ensures a good

wetting of the electrolyte, accommodates the volume changes along with the

discharge/charge reactions, and facilitates the fast diffusion of Na-ions as well. Mn3O4

thin film exhibits a similar structure as that in Fe2O3 film, with larger pores between

straighter grids (Figure 1c). There are also some minor cracks in the grids, which

might be harmful for the structure integration during cycling. In contrast to the

reticular structure of Fe2O3 and Mn3O4, Co3O4 film displays a different morphology,

6 / 19
with ~100 nm-diameter nanospheres distributed among cross-linked nanowires.

Besides, a few scattered nanoclusters can also be observed on the film (Figure 1e). As

for the NiO film, the morphology has transferred to the agglomeration of

spherical-like grains. (Figure 1g).

The electrochemical activity on Na-ion and cycling stability of the four TMO films

were evaluated at a constant current density of 100 mA g-1under galvanostatic

conditions. All the TMO film anodes considerably delivered the first discharge

capacities of 949 (Fe2O3), 257 (Mn3O4), 582 (Co3O4) and 744 mAh g-1 (NiO),

respectively. The Fe2O3 anode exhibits excellent cycling performance, with a

reversible capacity as high as 385 mAhg-1after 200 cycles, corresponding to 73%

capacity retention (Figure 1b). Similar to the Fe2O3 anode, the Mn3O4 film also

shows superior stability upon cycling, with 61% initial charge capacity over 200

cycles (Figure 1d). In contrast, the capacity decays continuously upon cycling either

in Co3O4 or NiO (Figure 1f and h). As stated, the reticular structure in both the Fe2O3

and Mn3O4 films might be beneficial for the relief of volume change and thus keep

the electrode integration during cycling, leading to a superior cycling performance

compared with Co3O4 and NiO.

For conversion-type anodes, a high potential hysteresis is observed due to the

energy penalty associated with the formation of nanoparticles in LIBs. Figure S3

presents the voltage profiles of the first two discharge/charge curves for the four TMO

anodes applying a current density of 100 mA g-1. It is found that the voltage hysteresis

of Fe2O3 and Co3O4 is roughly 0.75-1.0 V and 0.86 V between the characteristic

7 / 19
red-ox plateaus respectively, while a higher voltage hysteresis of NiO (1.12 V) and

Mn3O4 (1.30 V) is recorded, suggesting a faster sodium reaction kinetics for Fe2O3

and Co3O4 electrodes. To further explore the electrochemical behavior along with

Na-ion uptake/extraction, cyclic voltammetry (CV) was applied for the evaluation of

the Fe2O3anode, as shown in Figure 2a. The charge-discharge curves of the

Fe2O3anode are also included for comparison. During the first sodiation process, a

strong peak at 0.54 V is clearly observed. Correspondingly in the voltage profiles

(Figure 2b), a long plateau in the range of 0.9-0.6 V is also found. Considering the

fact that the galvanostatic battery test and CV can’t be operated in the exact same

condition, there might probably be a little variation between the peak position of CV

and the plateau range of voltage profile. Nevertheless, it can be concluded that the

strong peak at 0.54 V corresponds to the long plateau discharge, which might be

attributed to the reduction of Fe (III) to Fe (0). Additionally, in the second discharge

process, the reduction peak centered at 0.54 V has shifted to 0.65 V with an obvious

intensity drop, due to the decomposition of the liquid electrolyte and formation of an

SEI layer in the first cycle.

On the other hand, we have previously investigated the electrochemical behavior of

Fe2O3 electrode in LIBs system. The CV curves and voltage profiles of Fe2O3 in LIBs

are presented (Figure S5) in order to investigate the difference of electrochemical

behavior between SIBs and LIBs [30]. In the first lithiation process, there are two clear

peaks at 1.3 V and 0.72 V in accordance with the two plateaus in the voltage profiles,

indicating Li inserting into amorphous Fe2O3 and reduction of Fe (III) to Fe (0),

8 / 19
respectively. In the case of SIBs, only the last reaction occurred. Besides, the reduction

peak of Fe2O3 in SIBs is lower than in LIBs, which would provide a higher output

voltage and power density when applied in the full cell.

In the research of TMO based anodes for LIBs, there is a general understanding of

that the capacity is partly contributed from pseudocapacitance behavior as signaled by

the sloping curve that follows the conversion plateau in the discharge curve. In our

case of SIBs, a similar long sloping tail until the termination of discharge is also seen

(Figure 2b). To investigate the whether such pseudocapacitance-type behavior of

TMO based anodes exists in SIBs as well, a series CV curves at scan rates of 0.1-6

mV s-1 was measured for the Fe2O3 anode (Figure 2c). Upon increasing the scanning

rate, the current increases and the redox peaks vanishes gradually, finally leading to a

mirror-like-image shape, which is usually considered as a signature mark for

capacitance/pseudocapacitance-type behavior. From the liner relationship between the

current and scan rate (Figure 2d), we can extract a capacitance of ~572 F g-1

according to C=I/(dV/dt) g-1 [31,32]. Considering the limited electrical double-layer

capacitance, such a large value of capacitance further provides an affirmative

evidence of pseudocapacitance-type behavior, which might be caused by catalytically

enhanced electrolyte decomposition [31]. Based on the analysis above, we can

conclude that the pseudocapacitance-type behavior of TMO based electrodes also

contributes for the sodium storage, as characterized by the sloping tail in the discharge

profile and ~0.21 V broad peak in the CV curve.

9 / 19
 The morphological and compositional changes of the Fe2O3 film after discharge

and charge process are shown in Figure 3. After the complete discharge on 0.005V,

the initial reticular structure can’t be observed (Figure 3a), replaced by the crossed

nanoplates dispersing in the porous matrix of nanoparticles. The corresponding SAED

pattern (Figure 3b) shows diffraction spots/rings that are characteristic of three phases

including Na2O, metallic Fe and Fe2O3, indicating the occurrence of conversion

reaction during sodiation. The results show consistency with that of XPS investigation

(Figure S4). As shown in Figure 3a, the newly generated nanoplates might be

metallic Fe, surrounded by Na2O nanoparticles matrix. Besides, the presence of a

small quantity of Fe2O3 phase was caused by the oxidization of Fe in the air

atmosphere and/or incomplete reduction during Na insertion. When recharging back

to 3.0 V, the porous 3D reticular structure returned back as well as a fresh film

(Figure 3c), except for a few minor cracks observed. The SAED pattern also confirms

the complete oxidation of metallic Fe by the fact of only Fe2O3 phase indexable. The

residual Na2O phase might be caused by electrolyte decomposition, which has also

been confirmed in the previous report of α-MoO3 [26]. The SAED investigation and

above CV analysis clearly suggest the conversion reaction as follows:

Fe2O3+6Na++6e-↔2Fe0+3Na2O

In addition to the high reversible capacity and excellent capacity retention, the

Fe2O3 electrodes also display outstanding high rate capability (Figure 4a). The Fe2O3

electrode delivers specific capacities of 610, 561, 474, 418, 371 and 323 mAh g-1 at

current densities of 0.05, 0.1, 0.2, 0.5, 1.0 and 2.0 A g-1 respectively. Even cycled at an

10 / 19
ultra-large current density of 5.0 A g-1, a record capacity of 233 mAh g-1could still be

sustained, which exceeds most SIB anodes previously reported including nongraphitic

carbon and Na-alloy metals [15-26]. After cycling at high rates, a specific capacity as

high as 604 mAh g−1can be recovered when the current density is reduced back to 0.05

A g-1. Worthy of noting is that the anomalous Coulombic efficiency is observed at low

current density (50-100 mA g-1), which might be avoided by switching appropriate

electrolyte [33]. Furthermore, we also evaluated the long-term cycling performance of

the Fe2O3 anode at high current densities (Figure 4b). Interestingly, there are minor

capacity drops with the increase of the current density and the capacity kept rather

high and stable even after 200 cycles: 386 mAh g-1at 100 mA g-1, 331 mAhg-1 at 200

mA g-1 and 273 mAhg-1 at 1000 mA g-1. The pseudocapacitance-type behavior might

play a key role in the superior rate capability of TMO anodes, which inspires the

potential power application of SIBs in the future.

4. Conclusions

In summary, we have fabricated series of transition metal oxides including Fe2O3,

Mn3O4, Co3O4 and NiO, and characterized the relative electrochemical properties with

application of anodes for SIBs. The sodium uptake/extract was confirmed in the way

of reversible conversion reaction. The pseudocapacitance-type behavior was also

observed in the contribution of sodium capacity as that in previous reports on LIBs. A

large reversible capacity of 386 mAh g-1at 100 mA g-1 was maintained over 200

cycles; meanwhile, a high capacity of 233 mAh g-1 has been sustained even cycling at

a large current-density of 5 A g-1. The high reversible capacity, excellent cycling

11 / 19
stability and superior rate capability of the TMO electrode offer great potential

forward to develop high-performance SIB anodes reacting through conversion

reactions.

Acknowledgements

This work was supported by National Natural Science Foundation of China

(NSFC-21373184) and Doctoral Fund of Ministry of Education of China. Dr. Yinzhu

Jiang wishes to acknowledge an equipment subsidy offered by Alexander von

Humboldt (AvH) Foundation.

References

[1] M.E. Mann, R.S. Bradley, M.K. Hughes, Nature 1998, 392, 779-787.

[2] K. Tomabechi, Energies 2010, 3, 686-695.

[3] M. Winter, R.J. Brodd, Chem. Rev. 2004, 104, 4245-4269.

[4] C.J. Barnhart, S.M. Benson, Energy Environ. Sci. 2013, 6, 1083-1092.

[5] A.L.M. Reddy, S.R. Gowda, M.M. Shaijumon, P.M. Ajayan, Adv. Mater. 2012,

24, 5045.

[6] B. Kang, G. Ceder, Nature 2009, 458, 190-193.

[7] B. Scrosati, J. Hassoun, Y.K. Sun, Energy Environ. Sci. 2011, 4, 3287-3295.

[8] M.D. Slater, D. Kim, E. Lee, C.S. Johnson, Adv. Funct. Mater. 2013, 23,

947-958.

[9] V. Palomares, P. Serras, I. Villaluenga, K.B. Hueso, J. Carretero-Gonzalez, T.

Rojo, Energy Environ. Sci. 2012, 5, 5884-5901.

12 / 19
[10] S.P. Ong, V.L. Chevrier, G. Hautier, A. Jain, C. Moore, S. Kim, X.H. Ma, G.

Ceder, Energy Environ. Sci. 2011, 4, 3680-3688.

[11] S.W. Kim, D.H. Seo, X.H. Ma, G. Ceder, K. Kang, Adv. Energy Mater. 2012, 2,

710-721.

[12] Y.H. Lu, L. Wang, J.G. Cheng, J.B. Goodenough, Chem. Commun. 2012, 48,

6544–6546.

[13] S.M. Oh, S.T. Myung, J. Hassoun, B. Scrosati, Y.K. Sun, Electrochem. Commun.

2012, 22, 149-152.

[14] S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki, T. Nakayama, A.

Ogata, K. Gotoh, K. Fujiwara, Adv. Funct. Mater. 2011, 21, 3859-3867.

[15] D.A. Stevens, J.R. Dahn, J. Electrochem. Soc. 2000, 147, 1271-1273.

[16] K. Tang, L.J. Fu, R.J. White, L.H. Yu, M.M. Titirici, M. Antonietti, J. Maier, Adv.

Energy Mater. 2012, 2, 873-877.

[17] Y. Cao, L. Xiao, M.L. Sushko, W. Wang, B. Schwenzer, J. Xiao, Z. Nie, L.V.

Saraf, Z. Yang, J. Liu, Nano Lett. 2012, 12, 3783-3787.

[18] Q. Sun, Q.Q. Ren, H. Li, Z.W. Fu, Electrochem. Commun. 2011, 13, 1462-1464.

[19] L.F. Xiao, Y.L. Cao, J. Xiao, W. Wang, L. Kovarik, Z.M. Nie, J. Liu, Chem.

Commun. 2012, 48, 3321-3323.

[20] A. Darwiche, C. Marino, M.T. Sougrati, B. Fraisse, L. Stievano, L. Monconduit,

J. Am. Chem. Soc. 2012, 134, 20805-20811.

[21] Y.H. Liu, Y.H. Xu, Y.J. Zhu, J.N. Culver, C.A. Lundgren, K. Xu, C.S. Wang,

ACS Nano 2013, 7, 3627-3634.

13 / 19
[22] D.W. Su, H.J. Ahn, G.X. Wang, Chem. Commun. 2013, 49, 3131-3133.

[23] L. Wu, P. Pei, R.J. Mao, F.Y. Wu, Y. Wu, J.F. Qian, Y.L. Cao, X.P. Ai, H.X.

Yang, Electrochim. Acta 2013, 87, 41-45.

[24] R. Alcantara, M. Jaraba, P. Lavela, J.L. Tirado, Chem. Mater. 2002, 14,

2847-2848.

[25] S. Hariharan, K. Saravanan, V. Ramar, P. Balaya, Phys. Chem. Chem. Phys. 2013,

15, 2945-2953.

[26] S. Hariharan, K. Saravanan, P. Balaya, Electrochem. Commun. 2013, 31, 5-9.

[27] M. Valvo, F. Lindgren, U. Lafont, F. Bj refors, K. Edstr m, J. Power Sources

2014, 245, 967-978.

[28] H. Kim, D.-H. Seo, S.-W. Kim, J. Kim , K. Kang , Carbon 2011, 49, 326.

[29] S.-W. Kim, D.-H. Seo, X.H. Ma, G. Ceder, K. Kang, Adv. Energy Mater. 2012, 2,

710-721.

[30] Y.Z. Jiang, D. Zhang, Y. Li, T.Z. Yuan, N. Bahlawane, C. Liang, W.P. Sun, Y.H.

Lu, M. Yan, Nano Energy 2014, 4, 23-30.

[31] S. Laruelle, S. Grugeon, P. Poizot, M. Dolle, L. Dupont, J.M. Tarascon, J.

Electrochem. Soc. 2002, 149, A627-A634.

[32] R. Ding, L. Qi, M. Jia, H. Wang, Electrochim. Acta 2013, 107, 494-502.

[33] B. Koo, S. Chattopadhyay, T. Shibata, V.B. Prakapenka, C.S. Johnson, T. Rajh,

E.V. Shevchenko, Chem. Mater. 2013, 25, 245-252.

14 / 19
 (a)

1μm

(c)

1μm

(e)

1μm

(g)

1μm

Figure 1 SEM images of the as-prepared Fe2O3 (a), Mn3O4 (c), Co3O4 (e), NiO (g)
film, cycle performance of Fe2O3 (b), Mn3O4 (d), Co3O4 (f), NiO (h) at current density
of 100 mA g-1.

15 / 19
Figure 2 (a) The 1st, 2nd and 3th charge–discharge curve of Fe2O3, (b) CV curves of
Fe2O3 composite electrode at a scan rate of 0.1 mV s-1 for the first three cycles within
a potential range of 0.005 to 3.0 V (vs. Na/Na+), (c) CV curves for a Fe2O3/Na cell
that was initially discharged down to 0.005V. The cell was cycled between 0.005 and
1.8 V at scanning rates varying form 0.1 to 6 mV s-1, (d) The linear variation of the
current (taken as constant over 1.6 to 1.8 V voltage ranges) as a function of the scan
rate.

16 / 19
 (a) (b)

1μm

(c) (d)

1μm

Figure 3 SEM image and SAED patterns of Fe2O3 electrode after (a and b) first
discharge to 0.005 V vs. Na/Na+ and (c and d) first charge to 3.0 V.

17 / 19
 city(m
A
h
/g)
)9
8
7
6
0
5
(a /g
2
A
1A
.5
0 A
/g i0.
D
h
C 5a
esch
/
A rg

ecifC
a p
S
4
3
2
0
1 .5
0
2
/g
A
1 5
/g
A

0 1
0 m
u
ycleN
C
2
3
0 er04
b 0
5

Figure 4 Rate performances (a) and cycling performance (b) at different current
densities of 100, 200 and 1000 mA g-1.

Highlights:
1. A series of transition metal oxides is successfully demonstrated as anodes for
sodium ion batteries.
2. The sodium uptake/extract is confirmed in the way of reversible conversion
reaction.
3. The pseudocapacitance-type behavior is observed in the contribution of sodium
capacity.
4. For Fe2O3 anode, a reversible capacity of 386 mA h g-1 at 100 mA g-1 is achieved
over 200 cycles;
5. As high as 233 mA h g-1 is sustained even cycling at a large current-density of 5 A
g-1.

18 / 19
TOC graphic:

19 / 19
 (a)

µm
1µ

(c)

µm
1µ

(e)

µm
1µ

(g)

µm
1µ

Figure 1 SEM images of the as-prepared Fe2O3 (a), Mn3O4 (c), Co3O4 (e), NiO (g)
film, cycle performance of Fe2O3 (b), Mn3O4 (d), Co3O4 (f), NiO (h) at current density
of 100 mA g-1.

16 / 19
Figure 2 (a) The 1st, 2nd and 3th charge–discharge curve of Fe2O3, (b) CV curves of
Fe2O3 composite electrode at a scan rate of 0.1 mV s-1 for the first three cycles within
a potential range of 0.005 to 3.0 V (vs. Na/Na+), (c) CV curves for a Fe2O3/Na cell
that was initially discharged down to 0.005V. The cell was cycled between 0.005 and
1.8 V at scanning rates varying form 0.1 to 6 mV s-1, (d) The linear variation of the
current (taken as constant over 1.6 to 1.8 V voltage ranges) as a function of the scan
rate.

17 / 19
 (a) (b)

µm
1µ

(c) (d)

µm
1µ

Figure 3 SEM image and SAED patterns of Fe2O3 electrode after (a and b) first
discharge to 0.005 V vs. Na/Na+ and (c and d) first charge to 3.0 V.

18 / 19
 900 Discharge
(a)
Specific Capacity (mAh/g) 800 Charge
700 0.05A/g
0.05A/g
600 0.1A/g
500 0.2A/g
0.5A/g
400 1A/g
2A/g
300 5A/g
200
100
0
0 10 20 30 40 50
Cycle Number

Figure 4 Rate performances (a) and cycling performance (b) at different current
densities of 100, 200 and 1000 mA g-1.

19 / 19
*Graphical Abstract

TOC graphic: