Lithium antimonite: A new class of anode material for lithium-ion battery

doi:10.1016/j.elecom.2009.05.013

Electrochemistry Communications

Volume 11, Issue 7, July 2009, Pages 1389-1392

https://doi.org/10.1016/j.elecom.2009.05.013 Get rights and content

Abstract

LiSbO₃ has been synthesized by chemical mixing followed by thermal treatment at 800 °C. Field emission scanning electron microscopy revealed bar shaped multifaceted grains, 0.5–4 μm long and 0.5–1 μm wide, that cluster together as soft agglomeration. 2032 type coin cell vs Li/Li⁺ shows a flat charge–discharge plateau together with low Li intercalation/de-intercalation potential (0.2/0.5 V). A high discharge capacity of 580 mA h g⁻¹ has been obtained in the 1st cycle with 100% Coulombic efficiency. About 96% of the Coulombic efficiency is retained up to the 12th cycle, but at the 15th cycle, the Coulombic efficiency drops down to 88%. AC impedance spectroscopy shows an increase in electrolyte resistance (R_s) from 4.43 Ohm after the initial cycle to 12.4 Ohm after the 15th cycle indicating a probable dissolution of Sb into the electrolyte causing the capacity fading observed.

Introduction

There is a strong incentive to develop and characterize noncarbonaceous materials as anode for lithium-ion secondary batteries that deliver higher capacities than carbon (372 mA h g⁻¹). Inspired by the high theoretical Li intercalation capacity of antimony (660 mA h g⁻¹), several studies have been focused on metallic Sb or Sb/C composite anodes [1], [2], [3]. However, lithium intercalation in Sb induces a large volume expansion (137%) of the lattice resulting in drastic capacity fading [4]. To counter this volume expansion effect, intermetallic compounds, MSb_x, (1 < x < 3 and M = Ti, Mn, Fe, Co, Ni, Cu, Zn, In, Sn, etc.) have been investigated with the idea that the metal ion would act as an inert matrix [5], [6], [7], [8], [9], [10], [11], [12], [13]. However, the results show that although the volume expansion could be brought down to 4.4–49%, repeated cycling still leads to pulverization of the active particles and in capacity fading. Efforts have also been made to improve the reversibility in the Sb-based intermetallic electrodes by using compounds with special structures such as Cu₂Sb [14] or Mn₂Sb [7] where the lithiated and delithiated compounds have the similar structural relationship, but with limited success. Sb-based thin-films or nanosized materials have shown somewhat improved results as the structural shock due to volume expansion could be reduced in 2-dimensional structures [9], [15]. As an alternative to metallic Sb or intermetallics, Sb-oxides have also been considered [16]. The poor reversibility of Sb₂O₃ observed initially could only be improved in the form of thin film electrodes [15]. Among the other Sb-based materials, some studies are available on antimony phosphate, SbPO₄ [17], vanadium antimonite, VSbO₄ [18], bismuth antimonite, BiSbO₄ [19] but with poor specific capacity and cycle life. Therefore, it appears that although Sb has a high prospect as an anode material, its potential could not yet be successfully translated into development of a suitable electrode. During the course of experiments with Li₄Ti₅O₁₂/Sb composite anodes, we have found a new class of electroactive materials namely, the family of lithium antimonites (LiSbO₃ and LiSb₃O₈) which show encouraging results as lithium-ion battery anode with respect to a low intercalation potential and high discharge capacity. In this paper, for the first time, we report the electrochemical properties of LiSbO₃.

Section snippets

Experimental

A chemical process was adopted for the synthesis of LiSbO₃ powder. An aqueous solution of stoichiometric amounts of lithium nitrate (LiNO₃) and L-alanine (Merck, 99.0%) was mixed with hydrochloride solution of antimony sulfide (Sb₂S₅). The mixture was heated at a temperature of ∼150 °C on a hot plate with constant stirring by a magnetic needle. After evaporation of the solvent, a black mass was collected and further heat treated in air at 800 °C for 10 h.

X-ray powder diffractogram was recorded in

Results and discussion

There are a few reports available on the synthesis of LiSbO₃ by solid state method [20] and by ion-exchange process [21]. This perovskite type oxide has an orthorhombic crystal structure with an array of hexagonally closed packed oxygen atoms in which the cations occupy two-third of the octahedral sites. LiO₆ octahedra share faces to form a continuous string and each of the SbO₆ octahedra share two edges forming a continuous zigzag chain as shown in Fig. 1a [22]. The X-ray diffractogram of LiSbO

Conclusions

A new anode material, LiSbO₃, for lithium-ion battery is introduced. Flat charge–discharge plateau together with low Li intercalation/de-intercalation potential (0.2/0.5 V) versus Li and a specific capacity of ∼600 mA h g⁻¹ make it a very promising anode. The results may also stimulate investigation on other lithium antimonites such as LiSb₃O₈, Li₃SbO₄ etc as prospective anode materials.

Acknowledgement

The authors wish to thank Director, CGCRI for his kind permission to publish this work.

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Lithium antimonite: A new class of anode material for lithium-ion battery

Abstract

Introduction

Section snippets

Experimental

Results and discussion

Conclusions

Acknowledgement

Solid State Ionics

J. Power Sources

J. Power Sources

Mater. Lett.

J. Power Sources

J. Alloy. Compd.

Electrochem. Commun.

Electrochem. Commun.

Solid State Ionics

Solid State Ionics

J. Solid State Chem.

J. Power Sources