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Electrochemical and Spectroscopic Studies of Nanocomposites Laden with BaTiO3-grafted-graphene Oxide

The electrochemical behavior of lithium-sulfur batteries was investigated by means of electrochemical impedance spectroscopy (EIS). Films of NCPEs (PEO+LiCF3SO3+BaTiO3-g-GO) were cast using a novel hotpress technique. The addition of filler in fractional amount to the solid polymer matrix at room temperature further enhances the ionic conductivity. The membranes were subjected to cycling, FT-IR and Raman spectroscopic analyses. The occurrence of ion-ion pairs interaction has been identified using FT-IR and Raman analysis. Cells with this electrolyte have a high coulombic efficiency of 98% and a high cycling stability.


I. INTRODUCTION
The escalating demand for energy from transport and electronic sectors has prompted researchers to find alternative energy conversion/storage devices across the world 1 . Approximately 68% of today"s electrical energy is supplied from fossil fuels. The benefits of the lithium-ion battery, such as highenergy density, good performance, no-memory effect, high single cell voltage, and long cycle life have qualified lithium-ion batteries as ultimate power source for portable electronic devices such as digital cameras, laptop computers, mobile phones, etc., gave the battery a rapid acceptance in the market 6,7 . Lithium-sulfur (Li-S) energy storage, which can deliver a high theoretical energy density of 2600 Wh kg -1 , has been considered as one of the most promising candidates for the next-generation energy storage devices [8][9][10][11][12] . The high energy density is achieved by utilizing the high-capacity sulfur cathode (1672 mA h g -1 ) and lithium metal anode (3860 mA h g -1 ), as well as the lowest negative electrochemical potential of the anode (3.040 V vs. the standard hydrogen electrode. Furthermore, sulfur enjoys the advantages of abundant resources, low costs, and high biocompatibility, which are particularly attractive for reliable bulk energy storage applications [13][14][15][16][17][18][19] . The emergence of the Li-S battery is traced back to the 1960s, yet as compared to the rapid advancement of LIBs, it is still the incumbent technology 8,19 . Successful operation of Li/S batteries has been achieved through the development of composites of sulfur with carbonaceous 20-29 and polymeric 30-33 materials. In these composites, the S particles are embedded into the conductive carbon or polymer matrices 20,27,34 , which enhance the electronic conductivity of the composite and hinder the dissolution of polysulfides into the electrolyte [35][36][37][38] .
Another strategy to improve the capacity and cyclability of Li/S batteries is the electrolyte optimization so as to reduce the loss of sulfur by dissolution in the liquid electrolyte 36,[39][40][41][42][43] . Among the possible electrolyte modifications, replacement of the common liquid organic electrolytes with polymer electrolytes has proved promising and efficient.
Polymer electrolyte may generally be defined as a membrane that possesses transport properties comparable to that of common liquid ionic solutions 44 .
In the present study, the characterization techniques for Lithium sulphur batteries for various fillers and concentrations are studied. In the present work, a unique hybrid nanoparticle consisting of BaTiO3 which is chemically coupled to graphene oxide (GO) sheets was employed as a filler 46,47 . This hybrid particle was suitably incorporated in a PEO matrix along with a lithium salt to design polymer electrolytes for all-solid-state lithium-batteries and its spectroscopic and electrochemical properties are studied.

II. METHODS AND MATERIAL
A. Preparation of NCPE PEO-based nanocomposite polymer electrolyte (NCPE) were prepared by a novel dry (solution free) hot-press method as reported earlier 48 . Precursors used were, PEO,LiCF3SO3,BaTiO3-g-GO. The total weight of polymer, inert filler and lithium salt was set to be 100% by weight. The solution was continuously stirred in a magnetic stirrer for 6 hours at room temperature. The viscous solution was cast as a membrane. Upon evaporation of solvent the precursor was hot-pressed in order to get a uniform membrane. The thickness of the membrane was between 50-60µm. Subsequently, this membrane was stored in a vacuum oven for further characterization.