Low Cost Room Temperature Synthesis of NaV3O8.1.69H2O

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Low Cost Room Temperature Synthesis of NaV3O8.1.69H2O Nanobelts for Mg Batteries Muhammad Rashad, Hongzhang Zhang, Muhammad Asif, Kai Feng, Xianfeng Li, and Huamin Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b18682 • Publication Date (Web): 18 Jan 2018 Downloaded from http://pubs.acs.org on January 18, 2018

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ACS Applied Materials & Interfaces

Low Cost Room Temperature Synthesis of NaV3O8.1.69H2O Nanobelts for Mg Batteries

Muhammad Rashad

a, b

, Hongzhang Zhang

a, b

, Muhammad Asif c, Kai Feng

a, b

,

Xianfeng Li a,b*, Huamin Zhang a,b**

a

Division of Energy Storage, Dalian Institute of Chemical Physics, Chinese Academy

of Sciences, Zhongshan Road 457, Dalian 116023, China

b

Collaborative innovation Center of Chemistry for Energy Materials (iChEM), Dalian

116023, China.

c

Department of Materials Science and Engineering, College of Engineering, Peking

University, Yiheyuan Road 5, Beijing 100871, China

To whom correspondence should be addressed. Email: [email protected]; [email protected]

KEYWORDS: NaV3O8.1.69H2O nanobelts, Microstructural characterization, Magnesium battery, Electrochemical characterization, Energy storage.

ABSTRACT: Potentially safe and economically feasible magnesium batteries (MBs)

ACS Paragon Plus Environment

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have attracted tremendous research attention as an alternative to high cost and unsafe lithium ion batteries (LIBs). In current work, for the first time, we report a novel room temperature approach to dope atomic species sodium between the vanadium oxide crystal lattice to obtain NaV3O8.1.69H2O (NVO) nanobelts. Synthesized NVO nanobelts are used as electrode material for MBs. The MBs cells demonstrate stable discharge specific capacity of 110 mA h g-1 at a current density of 10 mA g-1 and a high cyclic stability i.e. 80% capacity retention after 100 cycles at a current density of 50 mA g-1. Moreover, the effects of cut off voltages (ranging from 2 to 2.6 V) on their electrochemical performance were investigated. The reason for limited specific capacity of MBs is attributed to the trapping of Mg ions inside the NVO lattices. This work opens up a new pathway to explore different electrode materials for MBs with improved electrochemical performance.

1. INTRODUCTION

Global energy crises has caused continuously increasing demands for potentially safe advanced energy storing devices with high energy and powder density

1-2

.

Rechargeable lithium ion batteries (LIBs) have been extensively employed as energy storage devices in electronics and electric vehicles owing to their high specific capacities and energy density during last two decades 3. Though, lithium ion battery technology has been commercialized and dominated the current market, however,


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their high cost, safety concern, and dendrites formation on lithium anode have inspired researchers to look for alternative options characterized by cheap, potentially safe, and dendrite free anode systems

4-5

. Rechargeable magnesium batteries (MBs)

have been considered as an ideal option with numerous advantages over lithium ion systems. For example, high natural abundance of magnesium metal, comprising 13.8% of earth crust compared to 0.0007% of lithium, therefore, lowering the cost of MBs. Moreover, magnesium metal anodes do not suffer with dendrite formation during recycling and possess high volumetric capacity of 3833 mAh cm-3 compared to 2062 mA h cm-3 for lithium. Likewise, relatively high melting temperature (660°C) and low volumetric density (1.74 g cm-3) of magnesium metal make the battery system much safer and lighter than the lithium based battery systems

6-8

. Despite of

these advantages, there are several challenges, which hinder commercialization of the MBs, such as passivation of anode film, low diffusion rate of Mg2+, low reversibility, high polarization, and low performance of cathode materials. On the other hand, low working voltage and chemical reactivity of electrolytes with commonly used metal (copper, nickel and aluminum) current collectors further hindered the development of MBs 9. Aurbach et al.

6

reported rechargeable MB prototype for the first time.

Afterwards, significant efforts have been made to explore new high performance cathode/anode materials

10-14

, and compatible electrolytes

15-17

for MBs. In recent

years, several compounds have also been explored for MB electrodes, which include cobalt sulfide (CoS) 18, molybdenum sulfide (MoS2) 14, 19, graphite fluoride (CF0.8) 20, birnessite manganese oxide (MnO2) 21, MgCo2O4 22, MgFePO4F 23, and MgFeSiO4 24.



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However, the electrochemical performance of MBs is still far from commercial applications due to their low voltages, specific capacities and complex synthesis techniques. Therefore, it is crucial to look for simple and green chemistry synthesis methods to fabricate electrode materials for MBs.

Vanadium pentoxide (V2O5) has emerged as a promising electrode material owing to facile ion movement across its layered framework, which results in significantly high specific capacities in LIBs

25-28

. For example, J. Xu et al.

29

and his coworkers

investigated electrochemical potential of nano/micro sized reduced graphene oxide (rGO) encapsulated vanadium oxides tablets for LIBs. These composites exhibited maximum specific capacity of 250 m Ahg-1 at a current density of 20 mA g-1. Similarly, V2O5 nanowires 31

30

, and vanadium oxide/Graphene mesoporous composite

in LIBs revealed high reversible capacity of 1006 mA h g−1 at 500 mA g−1 current

density, even after 300 cycles. In short, extensive researches have been carried out to investigate the chemistry, electrochemical properties of V2O5, and optimization of electrolytes for intercalation and insertion type electrode materials for LIBs.

Compared with vanadium oxide based LIBs, MBs exhibit high polarization due to strong interaction of Mg ions with the host vanadium oxide lattice. This may lead to high energy barriers during Mg ions insertion, ultimately results in low diffusion coefficients 8. With the intention of reducing the polarization and to increase reaction kinetics at electrode numerous tactics have been applied. For example, certain amount


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of water was introduced into Mg(ClO4)2-acetonitrile based electrolytes to attain charge shielding effect of water molecule that transformed Mg ions into less polarizing solvated ions 32. Although significant improvement in specific capacity and reaction kinetics was observed, however, undesirable water reacts with anode. Another approach is to use host materials containing water in their crystal lattices, however specific capacities faded away in just after few cycles due to removal of crystal water

33

. To expand the interlayer spacing of host material for interaction of

Mg ions, polyethylene glycol was used between layers of vanadium oxide during sol-gel synthesis. This approach resulted in significantly improved reversible Mg-ion capacities, however, is limited to few cycles 34. Recent studies reveal that insertion of Li ions into magnesium system is also effective to get high electrochemical performance of MBs 35-37. However, insertion of lithium salts into MBs system lowers the working potentials. Therefore, alternative strategies are required for synthesis of electrode materials with fast reaction kinetics for Mg ions during redox reactions.

Besides, doping of atomic species between the vanadium oxide crystal lattice has boosted the electrochemistry of V2O5

38-39

. Recent reports revealed complex and

multistep synthesis procedure for synthesis of sodium doped vanadium oxide nanostructures as shown in Table 1 40-44. Thus, overall performance of sodium doped vanadium oxide nanostructures electrode in LIBs and SIBs is far from commercial needs. Simply, room temperature and cost effective approach to dope sodium into V2O5 crystal lattice is needed to synthesize efficient electrode materials with high



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electrochemical performance. To address this challenge, we have proposed very simple approach to synthesize sodium doped vanadium oxide nanobelts at room temperature. We used commercial V2O5 as host material and NaCl as dopant species to fabricate NaV3O8.1.69H2O (NVO) nanobelts. One dimensional (1D) nanobelt structures have numerous advantages, which include high aspect ratio, and electron/ions flow along the belt axis, thus boosting up electrochemical conduction.

Table 1. Recent reports about NaV3O8 synthesis routes and their electrochemical performances for LIBs and SIBs. Synthesis Morphology

Precursors

Technique

Maximum

Applications

Ref.

120mAhg-1/80mAg-1

SIBs

[40]

Capacity/Applied current density

Nanosheets

Sol–gel route

V2O5,C2H2O4, NaNO3

Nanobelts,

Ball-milling

NH4VO3, NaF

275mAhg-1/30mAg-1

LIBs

[41]

In situ template

F127, Ethanol,

235mAhg-1/0.1Ag-1

LIBs

[42]

method

CH3COONa,

V2O5, NaOH

160mAhg-1/10mAg-1

SIBs

[43]

Hydrothermal

V2O5,C2H2O4,

220mAhg-1/30mAg-1

LIBs

[44]

method

NaOH

nanorods, microrods Nanoplatelets

NH4VO3, C2H2O4, Nanowires

Hydrothermal method

Nanoflakes

Herein, we report a simple route for the synthesis of NaV3O8.1.69H2O nanobelts, and synthesized nanobelts are used as electrode material in MB for the first time. The MB displayed a maximum specific capacity of 110 mA h g-1. In addition to physical analysis of the cathode material, a comprehensive electrochemical study for


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rechargeable MB system is performed, which includes rate capability, cycle performance, and cutoff voltage. Current work has achieved significant improvement in the specific capacity of the MB compared to previous reports, which is expected to serve a step forward towards the development of the MB technology.

2. EXPERIMENTAL SECTIONS 2.1 Synthesis of nanobelts: A simple, economical, and green chemistry strategy was employed to fabricate NVO nanobelts with vigorous stirring at 25°C. Commercially available V2O5 powder (5g) (99.0%, Damao Chemical Co. Ltd., Tianjin, China) was dissolved in 75 mL of 2 M sodium chloride solution in distilled water under constant stirring in an oil bath. The aqueous solution was stirred for 3 days at 25°C to get a brownish suspension. The obtained suspension is subjected to sonication for about 1 hour to isolate nanobelts from clusters. Then, the product was washed with distilled water and ethanol several times to remove un-doped sodium. Finally the product was collected with the help of centrifuge machine and dried at 70 °C for whole night. The final product, NaV3O8.1.69H2O nanobelts were used for the microstructural and the electrochemical characterizations.

2.2 Electrolyte preparation: All phenyl complex (APC) electrolytes were prepared by mixing phenyl magnesium chloride (2 M solution in tetrahydrofuran (THF), 99.0%, Aladdin) with 0.5 M aluminum trichloride THF complex (99.0%, Sigma-Aldrich, Shanghai, China) in an argon filled glove box (with water and oxygen contents

Low Cost Room Temperature Synthesis of NaV3O8.1.69H2O

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