NiFe2O4 nanocomposites: A promising anode material for high-performance lithium-ion battery

Accepted Manuscript One-pot ultrasonic spray pyrolysis mediated hollow Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites: A promising anode material for high-performance lithiumion battery Manab Kundu, Gopalu Karunakaran, Shilpa Kumari, Nguyen Van Minh, Evgeny Kolesnikov, Mikhail V. Gorshenkov, Denis Kuznetsov PII:

S0925-8388(17)32584-7

DOI:

10.1016/j.jallcom.2017.07.208

Reference:

JALCOM 42624

To appear in:

Journal of Alloys and Compounds

Received Date: 9 April 2017 Revised Date:

15 July 2017

Accepted Date: 21 July 2017

Please cite this article as: M. Kundu, G. Karunakaran, S. Kumari, N.V. Minh, E. Kolesnikov, M.V. Gorshenkov, D. Kuznetsov, One-pot ultrasonic spray pyrolysis mediated hollow Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposites: A promising anode material for highperformance lithium-ion battery, Journal of Alloys and Compounds (2017), doi: 10.1016/ j.jallcom.2017.07.208. 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 proof before it is published in its final 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.

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One-pot ultrasonic spray pyrolysis mediated hollow Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposites: A promising anode material

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for high-performance lithium-ion battery

Manab Kundu 1,*,#, Gopalu Karunakaran 2, 3, *,#, Shilpa Kumari1, Nguyen Van Minh2, Evgeny Kolesnikov2, Mikhail V. Gorshenkov4, and Denis Kuznetsov2 1

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Department of Material Science and Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway 2 Department of Functional Nanosystems and High-Temperature Materials, National University of Science and Technology “MISiS,” Leninskiy Pr. 4, Moscow, 119049, Russia 3 Department of Biotechnology, K. S. Rangasamy College of Arts and Science (Autonomous), Tiruchengode-637215, Tamil Nadu, India 4Department of Physical Materials Science, National University of Science and Technology “MISiS,” Leninskiy Pr. 4, Moscow, 119049, Russia *

Corresponding Author

E-mail: [email protected], [email protected]

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TEL: +47 735 51218

E-mail: [email protected], [email protected] TEL: +7-985-663-75-69

Both the author’s contributed equally to this work

ABSTRACT

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In this article, for the first time, we are reporting on the electrochemical lithium storage properties of hollow Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposites. The nanocomposites exhibit excellent cycling performance with a capacity of 661 and 460 mA h g-1 after 500 cycles at a very high rate of 300 and 1000 mA g-1, respectively. Such superior performance over other Fe based mixed metal oxides is produced by the combination of the composite and the hollow structures. In virtue of the excellent electrochemical performance, hollow Mg0.25Cu0.25Zn0.5

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Fe2O4/NiFe2O4 nanocomposites have huge potential as anode materials for the next-generation lithium ion batteries. Keywords: Ultrasonic spray pyrolysis; Nanocomposites; Energy storage and conversion;

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Electrochemical performance; Lithium-ion batteries.

1. Introduction

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Lithium-ion batteries (LIBs) have been recognized as the most promising energy storage device, and have gained substantial attention due to their high energy density, low gravimetric

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density and long cycle life [1]. Unfortunately, the commercial graphite based anodes suffer from low lithium storage capacity (372 mA h g-1 theoretically), poor rate performance due to slow Li+ intercalation kinetics and safety concerns [2]. In order to get rid of these limitations by improving both the energy and power density of batteries, it has become necessary to find

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alternative anode materials with higher lithium storage capacities and better rate performance [3]. To address these challenges, different metal oxides as well as sulphides has been proposed as alternative LIB anodes [4-14]. The high capacities governed are by electrochemical conversion

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reactions, made these anode materials interesting. Nevertheless, the conversion reactions in these anodes are associated with potential hysteresis and large volume changes leading to poor cycling

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stability [15].

In recent years, the research focus in the search for a new anode materials has gradually

shifted from the simple metal oxides (SMOs, metal oxides composed of one kind of metal cation) to mixed metal oxides (MMOs, metal oxides composed of different metal cations, stoichiometric or non-stoichiometric) [15]. In the last few years, many MMOs such as ZnCo2O4 [16], NiFe2O4 [17], FeCo2O4 [18], Co2Mo3O8 [19], MgFe2O4 [20], ZnMoO4 [21] and NiMnO3 [22] have been explored extensively. The improved electrochemical performance of MMOs 2

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compared to SMOs is due to the synergistic effect of multiple metal species and better electrical conductivity, gaining MMO based anodes more attention. Inspired by this concept, in this manuscript we establish for the first time experimental

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evidence on the electrochemical performance of the Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites, showing that they could serve as a novel anode for next generation Li-ion batteries (LIBs). Recently, spray pyrolysis has been successfully applied in the preparation of

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various electrode materials with impressive electrochemical performance. The resultant products are fine spherical particles with a uniform chemical composition and a narrow particle size

we

have

introduced

the

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distribution, and can be easily used for large-scale applications [23, 24]. Therefore, in this study, ultrasonic

spray

pyrolysis

process

to

prepare

hollow

Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites for an advanced electrode material for LIBs. The electrochemical lithium storage behavior of this novel anode material is demonstrated by charge-discharge,

cyclic

voltammetry

and

electrochemical

impedance

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galvanostatic spectroscopy.

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2. Experimental

2.1. Materials used and production of hollow nanocomposites nitrate

Fe(NO3)2.6H2O,

Nickel

nitrate

Ni(NO3)2.6H2O,

Copper

nitrate

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Iron

Cu(NO3)2.6H2O, Magnesium nitrate Mg(NO3)2.6H2O and Zinc nitrate Zn(NO3)2.6H2O, (AR grade) have been used for the preparation of precursor solutions. These precursor reactants were mixed at a concentration of 0.1M using water as solvent, (Milli-Q Water, Millipore, Germany). After filtering three times with a Whatman filter, the precursor solution was filled in the ultrasonic generator (DK, Mist Maker). Once the ultrasonic generator was turned on, it generates small aerosol droplets which are flowed through a silica reactor at a rate of around 16 L/min. The 3

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flow rate was maintained by using two flask pump (KNF Berger, D7911). The silicon reactor was maintained at a temperature of 1200 oC using a tube furnace (Nabetherme 20/250/13). After the complete generation of the aerosol, the ultrasonic generator and the furnace were allowed to

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cool to room temperature. After about 10 to 15 hours, the prepared nanocomposites powders were obtained from the pyrolysis collection chamber.

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2.2. Physical and electrochemical characterizations of the nanocomposties

The crystalline phase of the nanocomposite was identified by X-ray powder diffraction

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(XRD) analysis (Difray, Russia). The nanocomposite powder sample was filled in a cuvette with a smooth surface and placed over the sample locator for XRD analysis, which was performed using chromium as an X-ray source. The chemical bonds and elements of nanocomposites were revealed by using a Fourier transform infrared (FTIR) spectrophotometer (Nicolet, Thermo

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Scientific, USA). The sample was prepared using KBr (potassium bromide) powder and nanocomposites (under ratio of 1:100) and a thin pellet was prepared for FTIR analysis. To figure out the dimension and structure of the nanocomposites, field emission-scanning electron

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microscopy (FE-SEM, Zeiss Ultra 55 LE) and transmission electron microscopy (TEM, LEO 912AB) were used. For FE-SEM analysis, the composite power was dispersed in ethanol by

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ultra-sonication and a small drop was loaded on carbon tape followed by drying for 30 min. For TEM analysis, the sample was loaded on a copper grid. The elemental composition present in the nanocomposites was confirmed via Energy dispersive spectrum (EDS, X-MAX, EDX SSD, Japan). Nitrogen adsorption isotherms of the synthesized nanoparticles were analyzed by using a Nova 1200e analyzer (Quantachrome Instruments, USA). The surface area of the powder was calculated using the Brunauere-Emmette-Teller (BET) method. The pore size and pore volume were calculated using the Barrett-Joyner-Halenda (BJH) method. 4

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For electrochemical characterization, the electrodes were fabricated by conventional slurry coating method using copper foil as current collector. The slurry consisted of the synthesized Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites (70 wt%), acetylene black (20

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wt%) and polyvinylidene fluoride (PVDF binder) (10 wt%) in n-methyl pyrrolidinone (NMP) solvent. The typical loading mass of the electrodes was ~1.0 mg cm-2. 2016 type coin cells were assembled with these electrodes using Li metal as counter as well as reference electrode, LiPF6

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in EC: DEC (1:1 vol%) as electrolyte and Celgard 2300 as separator. Assembly was carried out within an argon filled glove box (M’BRAUN, Germany) where the moisture and oxygen levels

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were kept below 1.0 ppm. Cyclic voltammetry (CV), Electrochemical Impedance Spectroscopy (EIS) and Galvanostatic charge–discharge cycles were carried out at room temperature using a Biologic VMP3 battery tester. CV and Galvanostatic charge–discharge were performed in the voltage window of 0.0–3.0 V. EIS was carried out in the frequency range from 0.01 to 100,000

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3. Results and discussion

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Hz.

The nanocomposite was formed by spray pyrolysis. In this method, when the nitrate

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containing precursor solutions enter the furnace in the aerosol form, the high temperature leads to the evaporation of water molecules making the precursor molecules condense and form the nanocomposite. The resulting nanocomposite was collected from the powder collection chamber and further characterized by different techniques. The XRD pattern of the synthesized nanocomposite is shown in Fig. 1a. The major peaks for the obtained nanocomposites are ~38º, ~48º, ~55º, ~66º, ~74º, ~90º, ~100º, ~112º and ~130º which are found to be best matched with the Mg0.25 Cu0.25 Zn0.5 Fe2O4 phase JCPDS file no. 00-051-0384, confirming a cubic crystalline 5

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phase. Similarly, the peaks obtained at ~38º, ~48º, ~55º, ~66º, ~74º, ~90º, ~100º, and ~112º correlate with the NiFe2O4 phase JCPDS file no. 00-044-1485 which also shows that the obtained nanocomposites are cubic crystalline [25]. The morphology and microstructure were

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observed by FE-SEM (Figs. 1b and 1c). The surface of the particles is wrinkled and very similar to that of the dried plum, with clearly visible surface sunken holes. The measured particle diameter is between 300 and 500 nm. The EDS analysis shown in Fig. 1d confirmes that all five

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metals are present in the nanocomposites.

To analyze the distribution of Ni, Zn, Cu, Fe, Co and O in the nanocomposites, EDX

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elemental mapping was performed from a selected area marked with a green box in Fig. 2a and presented in Fig. 2c (i-vi). The observed line scan shown in Fig. 2b confirms the presence of all the elements and shows their distribution in the Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposites. To identify the three dimensional structure of Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4

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nanocomposites, TEM was carried out and the observed results are shown in Figs. 3 a and b. The contrast between the dark edges and pale intervals provide convincing evidence of the hollow interior structure. The measured particle size is in the range of 300 to 500 nm, which is in with

the

FE-SEM

results.

Fig.

3c

reveals

the

HRTEM

images

of

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agreement

Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 composites. The lattice fringe spacing of 0.251 and 0.253 nm

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can be ascribed to the (311) plane of NiFe2O4 and Mg0.25Cu0.25Zn0.5Fe2O4, respectively. It is worth to mentioning that this kind of hollow structure favors the diffusion of Li+ ions and offers high contact area between the electrode and electrolyte during the electrochemical reaction, hence display promising electrochemical properties as anode materials for lithium-ion batteries. FTIR spectrum shown in Fig. 3d confirms the presence of different elements and the corresponding functional groups. Absorption bands are observed at 3494, 2163, 1646, 1405,

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1328, 1024 and 809 cm-1. The band at 3494 cm-1 is due to the O-H bond, indicating the presence of water molecules [26]. The other bands which are represented at 2163, 1646, 1405, 1328, 1024 and 809 cm-1 are due to the bending vibration, stretching vibration, and absorption bands of

[27-30]. The

specific

surface

area

and

porosity

of

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different groups such as Ni-O, Zn-O, Cu-O, Fe-O, and Mg-O, respectively in the nanocomposites

Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4

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nanocomposites were measured by the nitrogen (N2) absorption–desorption isotherm, presented in Figs. 4 a and b. The calculated surface area of the nanocomposite is 10.706 m2 g−1. Fig. 4c

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shows the corresponding pore size distribution calculated by the Barrett-Joyner-Halenda (BJH) method, indicating a narrow pore size distribution centered at around 4 nm. The calculated pore volume is found to be 0.012 cm3 g-1. Such a porous nature could facilitate the diffusion of Li+ and electrolyte into the active materials and supply void space to accommodate the large volume

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variation during the charge–discharge process, thus boosting the lithium storage performance of these composite electrode materials.

To understand the electrochemical behavior of Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4

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nanocomposites when used as an anode material for LIBs, we investigated the Li uptake and release properties. CV tests were performed at a scan rate of 0.1mV s-1 and the first four cycles

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are presented in Fig. 5a. It is clear that the first cycle cathodic scan is slightly different from the following three cycles. In the first scan, a broad reduction peak can be observed at 0.5 V. In the subsequent cycles, the reduction peak shifted to 0.82 V. During all cycles of the anodic scan, a pair of peaks at 1.7 and 2.4 V are observed. No obvious peak position shifts are detected during cycling,

indicating

a

stable

framework

and

good

electrochemical

reversibility

Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites during repeated reactions with lithium ions.

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Fig. 5b shows the charge-discharge profiles for selected cycles recorded at a current density of 300 mA g-1 in the potential range of 0.0-3.0 V. The first discharge curve exhibits a long potential plateau at 0.85-0.52 V followed by a slope down to 0.5 V. In the reverse process,

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the first charge curve also presents one charge plateau at about 1.42-2.3 V. As a result, the initial discharge and charge specific capacities of Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites are 1066 and 703 mAh g-1, respectively, corresponding to a coulombic efficiency of about 66%. The

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irreversible discharge capacity is mainly attributed to the large-scale electrolyte decomposition during formation of the SEI layer [3]. After first cycle onwards, no obvious change in shape of

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charge-discharge curves can be found, indicating that the host structure for lithium storage can be maintained during long term cycling. The stable lithiation-delithiation behavior is consistent with the variation of peak current in CV curves as shown in Fig. 5a. All this evidence confirms that Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites can be used as reliable lithium storage

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materials.

As the cycling stability, especially at high rates, is a very important aspect for real time applications, the long-life properties of Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites are

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scrutinized at 300 and 1000 mA g-1. It is observed that there is a rapid decay in capacities from 680 and 580 mAh g-1 in the initial cycle to around 450 and 290 mAh g-1 (the 60th cycle). The

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capacities then increase continuously to 661 and 460 mAh g-1 at the current densities of 300 and 1000 mA g-1 respectively. The average columbic efficiency in both cases is approximately 99.8%, demonstrating a stable host structure of Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposite. Moreover, it is worth to mentioning that the electrochemical reaction with lithium-ions is almost reversible even at high rate, demonstrating the good lithium storage performance of Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites.

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It is interesting that the reversible capacity shows a tendency to decrease during the initial 50 ~ 60 cycles and thereafter it increases up to a certain value and then stabilizes. This behavior can be attributed to the formation/conditioning or reversible formation of a gel-like polymer due to

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electrolyte decomposition of the electrode [31-34]. Such phenomena have been reported in other SMOs and MMOs like CoO-Li2O thin-film composite [35], Fe3O4 [36], nano-flake Fe2O3[37], and ZnFe2O4 [38], Fe2O3 nano-particles [39] and (Co0.62Fe1.38)FeO4/NiCo2O4 nanoboxes [40] .

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The rate performance of Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposite at various current densities ranging from 50 to 1000 mA g-1 is presented in Fig. 6a. To assess the material’s of

capacity,

ten

cycles

were

tested

at

each

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retention

current

density.

For

Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposite, it exhibits superior rate performance with the average charge capacities of 690, 633, 543, 480, 424 and 367 mAh g-1 at 50, 100, 200, 300, 500 and 1000 mA g-1 respectively. When the current density is changed back to 100 mA g-1 after 60

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cycles, the charge capacity of the Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposite electrode recovers to 634 mAh g-1. Furthermore, the charge capacity remains at 640 mAh g-1 after 80 cycles. Charge–discharge curves at different current densities are shown in Fig. 6b. The plateaus

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corresponding to Li uptake and extraction can clearly be seen even at high current rates. Such impressive lithium storage at high current rates may be attributed to the hollow structure of the

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Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposite. The hollow nature not only allows the electrolyte to diffuse easily into the interior of the electrode and reduce the resistance of lithiumion diffusion, but also accommodates the large volume change during lithiation and delithiation. The high capacity achieved even at a high current density of 1000 mA g-1 implies that this type of electrode can be a promising candidate for high power applications.

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In

order

to

further

clarify

the

superior

electrochemical

properties

of

Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposite, impedance values were measured before and after the CV. As shown in Fig. 7a, in both cases, the Nyquist plots consists of a depressed

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semicircle in the high frequency followed by a straight line in the low frequency. The high frequency semicircle is related to the charge-transfer resistance (Rct) on the electrode-electrolyte interface. Whereas, the low frequency region corresponds to the semi-infinite diffusion of the Li

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ions in the electrodes. It is very clear that the Rct after four cycles has increased. This increase in Rct value can be explained by partial electrolyte decomposition on the electrode surface, leading

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to continuous growth of SEI film [41]. The similar results in corresponding Bode plots (presented in Fig. 7b) indicate that the impedances at all frequencies almost remained constant. The FE-SEM images with different magnification (in Fig. 8) show the morphology of Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 after 500 cycles at a current density of 1000 mA g-1. Although,

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due to the presence of binder and active carbon, the images are not as clear as as-synthesized composites, it is obvious that the original structure of Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 is maintained. Hence, the morphology is stable during the long term cycling process even at a very

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high rate of 1000 mA g-1, resulting in the excellent electrochemical performance of the new composite anode. The retention in morphology upon cycling with the hollow structured anode

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material is also demonstrated in other previous literature reports [42-44]. The superior lithium storage performance of the hollow Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4

nanocomposite is believed to result from the unique hollow nanostructural feature. The hollow interior morphology forms a smooth pathway for Li+ and electron diffusion, and in the same time the empty space serves as a reservoir for electrolyte, providing sufficient electrochemical reaction and decreased electrolyte diffusion resistance during the lithiation and delithiation

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processes. Moreover, the mesoporous shell, whilst providing a larger surface area towards Li+ and electrolyte, directs the volume expansion towards the inner hollow core during the lithiation, and during the delithiation, the morphology recovers. Thus, the hollow spheres can

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effectively alleviate the volume changes during the lithiation/delithiation processes for cycling stability. In addition, the hollow nanostructure can facilitate the electrolyte infiltration for faster electrochemical reaction during the repeated charge discharge process. The stable structure with

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high surface area enhanced the rate capability as well as cycling performance of hollow Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposite. The resulting nano composite anodes are thus

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expected to possess high capacity, high power, long cycle life and high Coulombic efficiency.

4. Conclusions

In this work, hollow Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposites were synthesized

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by a one-pot ultrasonic spray pyrolysis process and investigated for the first time with respect to the electrochemical performance. The nanocomposites exhibited excellent cycling stability (520 mAh g-1 at a very high rate such as 1000 mA g-1 even after 500 cycles) outperforming many

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other SMOs and MMOs. Hence, the hollow Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposite is a

view.

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highly promising new anode material from both a fundamental and application-based point of

Acknowledgement The work was carried out with financial support from the Ministry of Education and Science of the Russian Federation in the framework of increase Competitiveness Program of

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NUST "MISIS", implemented by a governmental decree dated 16th of March 2013, N 211. Authors The authors greatly acknowledge Katie McCay for her assistant in English editing to

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improve the paper quality.

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Figure Captions

Fig. 1 Characterization of nanocomposite a) XRD, b and c) FE-SEM under different

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magnification and d) Elemental analysis (EDS).

Fig. 2 a) FE-SEM micrographs, b) EDX line scan and c i-iv) the elemental mapping of O, Cu, Fe, Mg, Zn and Ni of the Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposites.

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Fig. 3 a, b) TEM observations c) HR-TEM image and d) FTIR spectrum of the Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposites.

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Fig. 4 a) BET surface area plot b) N2 sorption/desorption isotherms and c) the corresponding pore size distribution of the Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposites. Fig. 5 a) CV curves for the first four cycles at a scan rate of 0.1 mVs-1 between 0.01 V and 3 V; (b) cycling performance at the current rate of 300 and 1000 mA g-1 and (c) Galvanostatic charge-

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discharge profiles for selective cycles at a current density of 300 mAg-1. Fig. 6 a) Discharge capacities of Mg0.25Cu0.25Zn0.5Fe2O4/ NiFe2O4 nanocomposites anodes subjected to varying current densities between 0.01 and 3.0 V vs Li/Li+ and (b) Galvanostatic

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Research Highlights •

First report on Mg0.25Cu0.25Zn0.5Fe2O4/NiFe2O4 nanocomposites as anode for LIBs

• The nanocomposites are synthesized by one-pot ultrasonic spray pyrolysis process • The capacities are 661 and 460 mA h g-1 after 500 cycles at 300 and 1000 mA g-1

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• Superior performance is endowed by synergic effect and composite’s hollow structure