Chemical and microstructural modifications in LiPON thin films exposed to atmospheric humidity

Nimisha, C.S.; Rao, G. Mohan; Munichandraiah, N.; Natarajan, Gomathi; Cameron, D.C.

doi:10.1016/j.ssi.2011.01.001

Cited by 37 publications

(33 citation statements)

References 23 publications

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“…Hence, the transmission was taken prior to the SE measurements. It was reported that carbonate specie always appeared and increased with moisture air atmosphere exposure over the surface of LiPON film . However, the impedance measurements indicated that the ionic conductivity of our LiPON films showed almost no change after being exposed in air for 3 days, which means the bulk film does not change during exposure.…”

Section: Data Analysis and Resultsmentioning

confidence: 68%

Spectroscopic ellipsometry and optical transmission study of LiPON thin films prepared by RF sputtering

Zhang

Shokhovets

et al. 2016

Phys. Status Solidi B

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Lithium phosphorus oxynitride (LiPON) film with high ionic conductivity, low electronic conductivity and high transparency in UV–VIS range offers the possible applications as electrolyte for optical devices, e.g. electrochromic device. In this work, the optical properties of LiPON are investigated by means of variable‐angle spectroscopic ellipsometry (VASE) and optical transmission spectra. LiPON thin films with composition of Li3.13PO1.69N1.39 and ionic conductivity of 4.9 × 10−6 S cm−1 at room temperature were prepared by RF magnetron sputtering. Optical constants have been derived on multiple samples with film thickness from 400 to 2000 nm in the energy range of 0.58–5.5 eV. The optical bandgap (Eg) of LiPON film is shown to be 3.07 eV by a Tauc plot. It is found that when E < Eg the Urbach exponential decay of absorption is observed. The Urbach tail width at room temperature is estimated to be 0.361 eV for the LiPON film.

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Section: Data Analysis and Resultsmentioning

confidence: 68%

Spectroscopic ellipsometry and optical transmission study of LiPON thin films prepared by RF sputtering

Zhang

Shokhovets

et al. 2016

Phys. Status Solidi B

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“…[1] If the associated pH change deteriorates the performance of the solid electrolyte, the battery can no longer function properly. [8,9] Presently, nearly all studies on aqueous Li batteries have utilized a Li 1+x+y Al x Ti 2-x P 3-y Si y O 12 (LATP) glass ceramic (Ohara Inc., Japan) [10] as the solid electrolyte, [4,5,7,[11][12][13][14][15] which corrodes rapidly unless the pH value is maintained between 7 and 10. [4] However, few solid electrolytes show satisfactory performance in this regard; many of them (e.g., LiPON and most sulfides) simply decompose in aqueous environments regardless of the pH value.…”

mentioning

confidence: 99%

“…[4] However, few solid electrolytes show satisfactory performance in this regard; many of them (e.g., LiPON and most sulfides) simply decompose in aqueous environments regardless of the pH value. [8,9] Presently, nearly all studies on aqueous Li batteries have utilized a Li 1+x+y Al x Ti 2-x P 3-y Si y O 12 (LATP) glass ceramic (Ohara Inc., Japan) [10] as the solid electrolyte, [4,5,7,[11][12][13][14][15] which corrodes rapidly unless the pH value is maintained between 7 and 10. [16][17][18][19][20] If immersed in strongly basic solutions, the LATP decomposes and forms a high-resistance phase.…”

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confidence: 99%

Excellent Stability of a Lithium‐Ion‐Conducting Solid Electrolyte upon Reversible Li⁺/H⁺ Exchange in Aqueous Solutions

et al. 2014

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Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7 La3 Zr2 O12 garnet as a Li-stable solid electrolyte. The material underwent a Li(+) /H(+) exchange in aqueous solutions. Nevertheless, its structure remained unchanged even under a high exchange rate of 63.6 %. When treated with a 2 M LiOH solution, the Li(+) /H(+) exchange was reversed without any structural change. These observations suggest that cubic Li7 La3 Zr2 O12 is a promising candidate for the separator in aqueous lithium batteries.

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“…The degradation of LiPON seems to lead to ionically conductive phases such as Li 4 P 2 O 7 which also explains why the stability of LiPON seems to extend beyond what some thermodynamic calculations have suggested (Zhu et al, 2015;Richards et al, 2016). Reactions with ambient atmosphere have also been shown to reduce the conductivity of LiPON to 9.9 × 10 −10 S/cm through the release of PH 3 and NH 3 (Nimisha et al, 2011). Thus, while LiPON does show excellent stability against lithium dendrite penetration in ASSBs, both computational and experimental studies will be necessary to understand truly understand the limits of LiPON and compatible electrodes for ASSBs.…”

Section: Stability Of Liponmentioning

confidence: 95%

Emerging Role of Non-crystalline Electrolytes in Solid-State Battery Research

et al. 2020

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As the need for new modalities of energy storage becomes increasingly important, allsolid-state secondary ion batteries seem poised to address a portion of tomorrow's energy needs. The success of such batteries is contingent on the solid-state electrolyte (SSE) meeting a set of material demands, including high bulk and interfacial ionic conductivity, processability with electrodes, electrode interfacial stability, thermal stability, etc. The demanding criteria for an ideal SSE has translated into decades of research devoted to discovering new electrolytes and modifying their structure/processing to improve their properties. While much research has focused on the electrolyte properties of polycrystalline ceramics, non-crystalline materials (glasses, amorphous solids, and partially crystallized materials) have demonstrated unique advantages in processability, stability, tunability, etc. These non-crystalline electrolytes are also fundamentally interesting for their potential contributions toward understanding ionic conduction in the solid state. In this review, we first review a decade of advances in two distinct families of non-crystalline lithium-ion electrolytes: lithium thiophosphate and lithium phosphate oxynitride. In doing so, we demonstrate two pathways for non-crystalline electrolytes to address the barriers toward development of all-solidstate batteries, viz., interfacial stability and conduction. Finally, we conclude with some discussion of the development of fundamental models of ionic conduction in the non-crystalline state, including the ongoing debate between strong and weak electrolyte theories. Collectively, these discussions make a promising case for the role of non-crystalline electrolytes in the next generation of energy storage technology.

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Chemical and microstructural modifications in LiPON thin films exposed to atmospheric humidity

Cited by 37 publications

References 23 publications

Spectroscopic ellipsometry and optical transmission study of LiPON thin films prepared by RF sputtering

Spectroscopic ellipsometry and optical transmission study of LiPON thin films prepared by RF sputtering

Excellent Stability of a Lithium‐Ion‐Conducting Solid Electrolyte upon Reversible Li⁺/H⁺ Exchange in Aqueous Solutions

Emerging Role of Non-crystalline Electrolytes in Solid-State Battery Research

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Chemical and microstructural modifications in LiPON thin films exposed to atmospheric humidity

Cited by 37 publications

References 23 publications

Spectroscopic ellipsometry and optical transmission study of LiPON thin films prepared by RF sputtering

Spectroscopic ellipsometry and optical transmission study of LiPON thin films prepared by RF sputtering

Excellent Stability of a Lithium‐Ion‐Conducting Solid Electrolyte upon Reversible Li+/H+ Exchange in Aqueous Solutions

Emerging Role of Non-crystalline Electrolytes in Solid-State Battery Research

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Excellent Stability of a Lithium‐Ion‐Conducting Solid Electrolyte upon Reversible Li⁺/H⁺ Exchange in Aqueous Solutions