Ultra-thin LiPON films – Fundamental properties and application in solid state thin film model batteries

Nowak, Susann; Berkemeier, Frank; Schmitz, Guido

doi:10.1016/j.jpowsour.2014.10.202

Cited by 101 publications

(88 citation statements)

References 27 publications

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“…ion gun (Rau&Roth, 4 cm ∅ ) and an oscillating quartz balance to record the deposited thickness during sputtering. Schematic representation of the sputter chamber is presented elsewhere …”

Section: Methodsmentioning

confidence: 99%

Modulation of the Optical Properties of Lithium Manganese Oxide via Li‐Ion De/Intercalation

Joshi

Hadjixenophontos

Nowak

et al. 2018

Advanced Optical Materials

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a change in its optical constants during lithiation. However, a quantification of the optical properties and their tailoring via dis/charging has not been probed yet.The present study aims at the quantification of the optical constants, that is, the complex refractive index (CRI) and its change during intercalation by varying the lithium content of Li x Mn 2 O 4 from x = 0 to x = 1. Furthermore, an attempt is made to establish a link between this change in optical constants to the band structure of the material, learned from various sources. [11,15,[18][19][20][21] Similar characteristics have been reported for other electrochromic materials, such as Nb 2 O 5 , WO 3 , V 2 O 5 , and MoO 3, [22] which are known to change their optical properties, namely the real (n) and imaginary (k, or extinction coefficient) part of the CRI during an electrochemical reaction. In these materials, intercalation of charged species results in the generation of different electronic absorption bands in the optical spectrum or insertion of additional bound charges acting as harmonic oscillators. [22] For the present study, the reflection spectrum is measured at different stages of intercalation to clarify such electrochromic phenomenon. The measured spectra are evaluated to extract the CRI of the material for different lithium contents. Furthermore, an innovative method of recording the reflectance spectrum in situ during the electrochemical reaction is demonstrated (Figure 1c) that provides an additional time resolution to the spectrometry. Results Structural CharacterizationThe X-ray diffractogram (XRD) spectra of representative samples of LMO in the as-deposited and annealed states are shown in Figure 2a. No characteristic LMO diffraction peaks are observed for the as-deposited layer (bottom curve of Figure 2a). Only a small hump, observed at 61.98° (marked with *), could be due to the LMO structure corresponding to {440} planes. This reflection is very broad and shifted in comparison to the work of Wickhamt and Croft. [23] (JCP2 database) that predicts the position at 63.78°. The shape and the shift in the reflection suggest that the LMO layer is nanocrystalline and stressed, as it is usually the case for sputter-deposited layers.The optical response of lithium manganese oxide (LiMn 2 O 4 , LMO) on intercalation with Li ions is quantitatively characterized. For this purpose, a layer of LMO and a layer of platinum, acting as current collector/reflector, are deposited on oxidized silicon wafers. The active layer is structurally characterized using X-ray diffractogram and transmission electron microscopy. Well-defined intercalation states are prepared electrochemically and investigated by optical spectrometry in reflectance geometry. The measured dispersion curves are described by the Clausius-Mossotti dispersion equation to derive the complex refractive index as a function of wavelength and intercalation state. The observed variation of the effective resonant wavelength is consistent with the change in the band structure of LMO with l...

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Section: Methodsmentioning

confidence: 99%

Modulation of the Optical Properties of Lithium Manganese Oxide via Li‐Ion De/Intercalation

Joshi

Hadjixenophontos

Nowak

et al. 2018

Advanced Optical Materials

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“…To some extent, the LiPON film has the advantage of forming contact with electrodes and they can meet the requirements of compact batteries. However, these abovementioned LiPON films exhibit relatively common conductivity levels and poor mechanical properties …”

Section: Synthesismentioning

confidence: 99%

Promises, Challenges, and Recent Progress of Inorganic Solid‐State Electrolytes for All‐Solid‐State Lithium Batteries

et al. 2018

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All-solid-state lithium batteries (ASSLBs) have the potential to revolutionize battery systems for electric vehicles due to their benefits in safety, energy density, packaging, and operable temperature range. As the key component in ASSLBs, inorganic lithium-ion-based solid-state electrolytes (SSEs) have attracted great interest, and advances in SSEs are vital to deliver the promise of ASSLBs. Herein, a survey of emerging SSEs is presented, and ion-transport mechanisms are briefly discussed. Techniques for increasing the ionic conductivity of SSEs, including substitution and mechanical strain treatment, are highlighted. Recent advances in various classes of SSEs enabled by different preparation methods are described. Then, the issues of chemical stabilities, electrochemical compatibility, and the interfaces between electrodes and SSEs are focused on. A variety of research addressing these issues is outlined accordingly. Given their importance for next-generation battery systems and transportation style, a perspective on the current challenges and opportunities is provided, and suggestions for future research directions for SSEs and ASSLBs are suggested.

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“…Thin‐film batteries with two‐dimensional electrode/electrolyte interfaces have relatively low interfacial resistances compared to bulk‐type solid‐state batteries, where the interfacial reactions are limited due to the small contact area between the particles . In contrast, Li 3 PO 4 and LiPON, which are typical electrolyte materials for thin‐film batteries, exhibit low ionic conductivities in the order of 10 −6 ‐10 −8 S/cm. Thus, lithium diffusion in the electrolyte layer is the rate‐determining step in thin‐film batteries.…”

Section: Introductionmentioning

confidence: 99%

Effect of excess Li₂S on electrochemical properties of amorphous li₃ps₄ films synthesized by pulsed laser deposition

et al. 2016

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Amorphous Li3PS4 films were synthesized by pulsed laser deposition (PLD) at room temperature using Li3PS4 targets with excess lithium and sulfur. Raman and X‐ray photoemission spectroscopies indicated that the Li3PS4 film synthesized with a stoichiometric amount of Li3PS4 target contained lithium‐deficient phases such as Li4P2S6, Li2−xS and sulfur due to composition deviation caused during the ablation process. The film synthesized with a 14% Li2S‐excess target (Li3.42PS4.21) contained fewer impurities, and exhibited a higher ionic conductivity of 5.3 × 10−4 S/cm at 298 K than the lithium‐deficient film (3.1 × 10−4 S/cm). The target composition is an important factor for the fabrication of highly conductive Li3PS4 films for electrolytes in thin‐film batteries.

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Ultra-thin LiPON films – Fundamental properties and application in solid state thin film model batteries

Cited by 101 publications

References 27 publications

Modulation of the Optical Properties of Lithium Manganese Oxide via Li‐Ion De/Intercalation

Modulation of the Optical Properties of Lithium Manganese Oxide via Li‐Ion De/Intercalation

Promises, Challenges, and Recent Progress of Inorganic Solid‐State Electrolytes for All‐Solid‐State Lithium Batteries

Effect of excess Li₂S on electrochemical properties of amorphous li₃ps₄ films synthesized by pulsed laser deposition

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Ultra-thin LiPON films – Fundamental properties and application in solid state thin film model batteries

Cited by 101 publications

References 27 publications

Modulation of the Optical Properties of Lithium Manganese Oxide via Li‐Ion De/Intercalation

Modulation of the Optical Properties of Lithium Manganese Oxide via Li‐Ion De/Intercalation

Promises, Challenges, and Recent Progress of Inorganic Solid‐State Electrolytes for All‐Solid‐State Lithium Batteries

Effect of excess Li2S on electrochemical properties of amorphous li3ps4 films synthesized by pulsed laser deposition

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Effect of excess Li₂S on electrochemical properties of amorphous li₃ps₄ films synthesized by pulsed laser deposition