Superionic Solid Electrolyte Li7La3Zr2O12 Synthesis and Thermodynamics for Application in All-Solid-State Lithium-Ion Batteries.

Daniil Aleksandrov,Anatoliy Popovich,Pavel Novikov,Qingsheng Wang

doi:10.3390/ma15010281

Daniil Aleksandrov, Anatoliy Popovich + Show 2 more

Open Access

https://doi.org/10.3390/ma15010281

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Abstract

Solid-state reaction was used for Li7La3Zr2O12 material synthesis from Li2CO3, La2O3 and ZrO2 powders. Phase investigation of Li7La3Zr2O12 was carried out by x-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS) methods. The thermodynamic characteristics were investigated by calorimetry measurements. The molar heat capacity (Cp,m), the standard enthalpy of formation from binary compounds (ΔoxHLLZO) and from elements (ΔfHLLZO), entropy (S0298), the Gibbs free energy of the Li7La3Zr2O12 formation (∆f G0298) and the Gibbs free energy of the LLZO reaction with metallic Li (∆rGLLZO/Li) were determined. The corresponding values are Cp,m = 518.135 + 0.599 × T − 8.339 × T−2, (temperature range is 298–800 K), ΔoxHLLZO = −186.4 kJ·mol−1, ΔfHLLZO = −9327.65 ± 7.9 kJ·mol−1, S0298 = 362.3 J·mol−1·K−1, ∆f G0298 = −9435.6 kJ·mol−1, and ∆rGLLZO/Li = 8.2 kJ·mol−1, respectively. Thermodynamic performance shows the possibility of Li7La3Zr2O12 usage in lithium-ion batteries.

Highlights

The commercial history of the lithium-ion battery was started in 1991 by Sony [1]
Atocdcoifrfdraincgtioton diffraction data, LLZOdahtaas, aLLI4Z1O/achdasspaaIc4e1/garocdups.pTahcee gvreorutipca. lTlhineevsearttitchael lbinoettsoamt tahreebroeltatotemd atorePrDelFated to PDF #00-064-0140
The thermodynamic characteristics were determined for Li7La3Zr2O12 solid-state electrolyte material for lithium-ion battery

Summary

Introduction

The commercial history of the lithium-ion battery was started in 1991 by Sony [1]. Since a lot of effort has been directed to improving the electrochemical performance of lithium-ion batteries [2]. Though LLZO has lower ionic conductivity in comparison with organic liquid electrolyte (~10−4 versus ~10−2 S·cm−1, respectively [9]), it provides high safety performance, high chemical stability against metallic lithium, a wide electrochemical potential window, low electronic conductivity, and high stability with moisture in the air; LLZO prevents lithium dendrite growth due to high mechanical strength [11,12,13,14,15]. Since as LLZO was first synthesized by Murugan et al [16], it was investigated to improve its chemical and structural stability, long life cycle, electrode/solid electrolyte. Since as LLZO was first synthesized by Murugan et al [16], it was investigated to improve its chemical and structural stability, long life cycle, electrode/solid electrolyte interface interactions, and high energy density at room temperature. TAM IV MTiAcrMocaIVlorMimicertoecral(oTrAimIentsetrru(TmAenInts,trSuhmaenngthsa, iS,hCahnignhaa)i,wCahsinuas)edwafosrucseadlofroi-r calorimetmetric inversitciginavtieosnti.gMateiaosnu. rMemeaesnutrpemareanmteptaerasmweetreersaswfoerlleoawssf:otlelomwpse:rtaetmurpeeirsa2tu98reKi,sv2o9l8- K, volume ume of theocfeltlhies c2e0llmisL.2A0 nmaLq. uAenouasqusoelouutsiosnolouft1iomnoolf·d1mm−3oHl·dCml w−3asHfCilllewd ains fithlleeadminpothueleampoule at at calorimectrailcocriemll.eTtrhice cdeislls.oTluhteiodnispsroolucetisosnofptrhoeceLsLsZoOf tphoewLdLeZrOwpaos wstadretredwafstesrtatrhteerdmaaflter thermal equilibriumeqwuailsibersiutamblwishaesde.stDabislsisohluedti.oDn iesnsothluatlipoyn veanltuhealwpyasvaolbuteaiwneads ofrbotamintehderfmroomeltehce-rmoelectrotromotive fmorocteivdeaftoardceurdinatgatdhuerdinisgsothluetidoinssporluoctieosns,pprroocveisdsi,npgrothveidhineagttdhiesshoelauttidoinsscoulurvtieo.n curve

Results

The Isobaric Heat Capacity

Entropy

The Standard Gibbs Free Energy

Conclusions