International Journal of Innovations in Engineering and Science, Vol. 2, No.1, 2017

e-ISSN: 2456-3463 International Journal of Innovations in Engineering and Science, Vol. 2, No.1, 2017 www.ijies.net Keywords- Alkali ion as super ionic conductors, solid state conducting glasses. The battery, ionic current interest in conductivity, glassy solid electrolytes STUDY OF electropositive ion, is due to two main amorphous solid reasons.[a].Since they ELECTRICAL electrolyte, lithium are X-ray amorphous, borate glass base solid there is wide scope for CONDUCTIVITY OF electrolyte. structural investigation on microscopic level INTRODUCTION leading to theoretical LITHIUM BORATE understanding of these The recognition of fast of these materials.[b] lithium conduction in IONICALLY Due to their advantage solids dated from 1921, [4] over their when Benrath and crystalline counter CONDUCTING Deokopf [1] discovered parts, they have good high temperature alpha prospects for being phase of Li SO until GLASSES 2 4 used in technological the 1940.New emphasis applications. The ionic has been given to this transport in amorphous area in 1967 as a result solid electrolyte has of discovery of the been reviewed by higher Li+ conductivity M .D. Mehare Souquet [5] in 1 in the alumina type Assistant Professor 1981.The fast ion layered structure. The Priyadarshini Indira Gandhi College of Engineering, conducting lithium state of knowledge of Nagpur, INDIA glasses have been Sodium lithium ion reviewed by Kulkarni conductors up to 1970 et al [6]. Progress in Abstract – Alkali ion weight than sodium or has been reviewed by fast ions glasses has conductors are of potassium. It is also Pizzine [2].About the been given by considerable interest more electropositive same time it become Minami[7] several because of their and thus, provides the evident that lithium is glassy electrolyte possible applications greater cell voltage potentially a highly system has been in solid state battery than other two ions. attractive element to discusses systems. The highly Lithium has additional use in kind of energy electropositive alkali advantage that it can storage system. Its light I.1 LITHIUM ion provides the be handling more weight and high electro BORATE GLASS possibility of large cell easily at room positivity as well as SYSTEMS voltage and very high temperature than other relative ease with energy densities. In alkali metals. On the which it may be These glasses are general, particular basis of theoretical handled have led to the comprised of a network material will be background and proposal of many lower former B2O3 in which required to act as considering the battery configurations the covalent bond either an electrode or advantage of utilizing both liquid and structure ensured the an electrolyte. Both amorphous solid solid electrolyte. rigidity of the application required electrolyte it was During the sane macromolecular high ionic thought imperative to decades, glasses structure and network conductivity, develop a lithium electrolyte with high modifier preferably at ambient borate glass base solid ionic conductivity have (Li2O,Na2O,K2O,Ag2O, or relatively low electrolyte. been found accidentally CaO,BaO etc) which temperature. Lithium Kunze in 1973 introduce ionic bond has a lower equivalent [3].which where refer giving rise to cationic 1 e-ISSN: 2456-3463 International Journal of Innovations in Engineering and Science, Vol. 2, No.1, 2017 www.ijies.net conduction.All oxygen The NMR investigation 725K. The mixed alkali glasses have been remain covalently for the borate glass effect on the spectra of prepared by Solgel bonded to cations of the added with different Ni2+ and Cu2+ on technique.The forming oxides in the alkali oxide modifier borate glasses has been enhancement in the elementary units. The shows different reported by Ahmed et conductivity in sulphide micromolecular are structural variation for al[30]. glasses (Li2O: SiO2 : thus formed by the each oxide [8].In GeS2) has been assembly of three units general the properties I.3 MIXED GLASS represented by in which at least one of exhibiting the mixed FORMER Deshpande et al and the oxygen ions, called alkali effect typically SYSTEMS: phenomenon called as bridging ion is shared reach either minimum It has been reported mixed glass former with other non-bridging or maximum depending [31-32] that for the effect ( MGFE ). oxygen carrying upon the specific some molar ration effective negative property with between lithium oxide I.4.GLASSES WITH charge and therefore substitution of second glass former (B2O5+ ADDITION OF maintain in their alkali e.g. electric P2O5), the ionic SALTS: vicinity alkali or resistivity .This conductivity, at room For increasing the ionic alkaline cations of the behavior for properties temperature conductivity of network modifier related to alkali ion substantially higher in glasses,different oxide. These ionic movement found borophosphate glasses approaches have been bonds are generally essentially independent than in pure borate or adopted .Of all the assumed to be of glass forming oxide phosphate.Tatsumisago approaches, the randomly distributed being observed in et al have studied the addition of lithium salt over the silicate [12-16], borate glass forming viz. halides,sulphates,to macromolecular chain [17-20],borosilicate conductivity and lithium conducting [5-6].Otto [8] was the [21],Phosphate [22-24] thermal properties of glasses has been well first to report glasses and germinate [25-26] glasses containing high established and widely with high lithium ion glasses. For mixed amount of Li2O in studied one.In 1966 conductivity at alkali glasses, the large Li2O: SiO2 : B2O3 , Otto [9] has reported relatively low maximum in electrical Li2O: B2O3 :P2O5, Li2O: that considerable temperature in resistivity has been P2O5 : SiO2 systems. amount of LiF,LiCl or

M2O:B2O3:SiO2 reported [27].Han et al According to them, the Li2SO4 could be (M=Li,Na) system. He [28] have studied the widest glass forming incorporated in lithium also suggested that high diffusion of Na+ and region has been glasses without + lithium ion Ag in binary observed in Li2O: SiO2: devitrifying them.Shue conductivity could be Na2O:B2O3 glasses. The B2O3 system. The and Tuller have obtained in borate electrical conductivity composition examined the effect of glasses if more that 40 for 4-24 mole% of dependence of CaO addition to Li2O : mole% lithium Na2O has been conductivity has been LiCl : B2O3 glasses, compounds could be measured from 373 oC found to be closely since such addition incorporated in the to the temperature related to Tg. The have been believed to glass without slightly below Tg. enhancement in improve the durability diversification. As a Matusita et al [29] have conductivity, mixing of in contact with general rule, the measured the electrical two glass forming lithiumCaO additions conductivity of oxide conductivity of [a] (1 – oxide, also observed in systematically glasses increases with X) Li2O :XbaO : 2SiO2 Li2O: SiO2: B2O3 decreases ionic increasing amount of [b] (1 – X) Li2O glasses containing large conductivity in network modifier such :XmgO : 2SiO2 [c] (1 – amount of Li2O. Tsai boroacite nad as Li2O,Na2O and K2O X) Li2O :XcaO : 2SiO2 and Greenblatt have metaborate glass

[9-11]. [d] (1 – X) Li2O :XBaO investigated the systems,the lithium

: 2SiO2 in the conductivity,IR and choride, which

I.2 MIXED ALKALI temperature rang from TMA for Li2O: SiO2 : systematically increases

GLASS SYSTEMS: room temperature to P2O5 system. These the conductivity,widens 2 e-ISSN: 2456-3463 International Journal of Innovations in Engineering and Science, Vol. 2, No.1, 2017 www.ijies.net to calcium doping.The Li2O conductivity (ϭ bulk) is hysteresis shown in glass in ternary system 1 I1 0 42.5 very important. ϭ bulk of fig.3 Li2O : (LiCl2):B2O3 each sample excluding (LCB) have been electrode effect, was examine by Raman 2 I2 0.08695 42.5 determined from the and NMR real axis intercept of 3 I3 0.1739 42.5 [ technique.The the complex impedance 4 0.3478 42.5 enhancement of the I4 analysis. It is also lithium conduction in 5 I5 0.05217 42.5 excludes the borate glasses by contribution of addition of LiCl has displacement current. also been observed by The initial ingredient Fig.3 The plot of log 3 Muller et al . were kept at kept at (ϭT) Vs 10 /T for 42.5 100oC for 24 hours to Li2O : 57.5 B2O3 : 0 II EXPERIMENTAL remove the moisture SiO2 TECHNIQUE: and were weighted as From the above result it Material Preparation: per molar ration with an is clear that the For the glass accuracy of 0.00001 g conductivity does not preparation using AE136 mettler follow the same path compositional (Switzerland) monopan during heating and parameter ‘n’ and ‘y’ electronic Balance. cooling cycle, are defined to have After grinding them Fig.1 Arrhenius plots moreover they exhibit systematic variation in thoroughly in acetone for Li O: B O : SiO different slop indicating former and modifier. for homogeneity, then 2 2 3 2 mixed former system attenuation in activation = dried mixture kept (Series-I) enthalpy. furnace at 400oC for 2 hour, then temperature II] o In the present work two increase to 600 C and CONCENTRATION different series are maintain at 1 hour. DEPENDENT prepared with general After evolution of CONDUCTIVITY: composition 42.5Li2O decomposition product

– (57.5-X) B2O3 – the melt was kept at The variation of o XSiO2. The series is 900-1050 C for 30 conductivity as a specified with minute then viscous function of Y for series constancy of Li2O melt was quenched in I and II are given in content given in table I aluminum block kept at figure 4 and 5 and II room temperature .The Fig.2 Arrhenius plots

quenching rate offered for Li2O: B2O3: SiO2 S. Glass Y Compositionby theof mole% two blocks was mixed former system No No found to be (Series-II) Li O 2 approximately 1 I1 0 42.5 102C/s .The prepared A detailed structure characteristic of entire 2 I2 0.08695 42.5 sample were studied by electrical LB series has revealed 3 I3 0.1739 42.5 characterization. the complete 4 I4 0.3478 42.5 amorphousness of the 5 I5 0.05217 42.5 III .RESULTS AND composition. The study Fig4 Variation of DISCUSSION: of an temperature conductivity as a dependent conductivity function of Y for series I] AC Conductivity: for this glasses, (I) at (250 oC) measured during S. Glas Y Composition Forof mole% the electrochemical No s No device, bulk heating and cooling, so as to see the thermal 3 e-ISSN: 2456-3463 International Journal of Innovations in Engineering and Science, Vol. 2, No.1, 2017 www.ijies.net A.Paul,Bull.Mat.Sci.,6. Cryst.Solids.15, [30] A.A.Ahmed and (1981),201. (1974),215 A.F.Abbas and [4] T.minami,J.Non- [23] H.M.Vyas and F.A.Moustaffa,Phys.and Cryst.Solids,95 and 96, J.M.Stevels,J.Non- Chem .of Glasses,24, (1981),107. Cryst.Solids.16, (1983).43 [5] W.A.Weyl,The Glass (1974),46 [31] G.Chiodelli,A.Magistris Industry (1948),200. [24] R.F.Bartholomew,J.Non and M.Villa, Solid State [6] O.P.Button,R.tondon,C. -Cryst.Solids,12, Ionics,18 & 19, King,M.H.Velez,H.L.T (1973),321 (1986),356 uller [25] A.V.Ivanov,Sov.Phys.S [32] A.Magistris andD.R.Uhlmann,J.Non olid States,5, .G.Chiodelli, and Cryst.Solids,49, (1964),1993 M.Villa, J.power Fig.5 Variation of (1982),129 [26] K.K.Evestropley and Sources, 14 ( 1975),307 conductivity as a [7] Y.Ito,K.Miyauchi and V.K.Pavloski,Structure T.Oi.J.Non- of function of Y for series Cryst.Solids,57, Glass,Vol.7( Consultant o (II) at (250 C) (1983),389. s Bureau,New York) [8] P.J.Bray and J.G.O (1966),103 It is seen from these Keefe,Phys.Chem.Glass [27] D.E.Day,J.Non- curve that for each es,4,(1963),37. Cryst.Solids,21(1976),3 series, characterize by a [9] K.Otto,Phys.Chem.Glas 43 [28] Y.H.Han, N.J.Kreidl specific values of n , ses.7(1),(1966),29 [10] A.E.Owen,J.Non- and D.E.Day, J.Non- the sample with y = Cryst.Solids,25(1977),3 Cryst.Solids, 30, 0.1 gives the maximum 70 (1979),241 conductivity. For the y [11] K.Huges and [29] K.Matusita,S.Takayama ≥ 0.2 the conductivity J.O.Isard,in Physics of and S.Sakka,J,Non- decreases. electrolyte ,Vol.1 , Cryst Solids ,40 (1972) (1980) ,149 IV] CONCLUSION: .ed.J.Haladik,Academic press,London,355. [12] R.M.Hakim and The glasses prepared by D.R.Uhlmann,Phys.Che quenching technique m.Glasses,8,(1967),174 are found to be ionic [13] G.J.Peddle,J.Soc.Glass. conductors. Amongst Tech.,18,(1921),195 the entire sample [14] B.Lengyel,Glastech.Ber studied the glass with .,18,(1940),177 [15] J.P.Pool,Verres et 42.5Li2O:57.5B2O3:0Si refract,2,(1948).222 O2 composition exhibits [16] J.O.Isard,J,Non- maximum conductivity. Cryst.Solids,1, Also, this composition (9169),23 may find potential [17] M.Coenen,Glastech application as solid Ber.,35(1962),14 electrolyte in [18] H.Rotger,Glastech electrochemical Ber.,31(1948),54 [19] K.A.Kostanyan,Structur devices. e of glass,Vol.2( Consultants Bureau ,New York) (1960),234 REFERENCES [20] R.L.Myuller,Sov.Phys.S olid State,2(1960),1219 [1] D.Rvaine,J.Non- [21] O.V.Mazurin,Structure Cryst.Solids,75, of (1985),3. Glass,Vol.4( Consultant [2] J.L.Souquet,Ann.Rev.M s Bureau,New York) ater.Sci.,11,(1981),211. (1965),5 [3] A.R.Kulkarni,H.S.Maiti [22] H.M.Vyas and and J.M.Stevels,J.Non-