Thin Film Amorphous Electrolytes: The Li2O-SiO2-P2O5 System

Bates, J.B.; Dudney, Nancy J.; Sales, B. C.; Robertson, J. D.; Zuhr, R. A.; Gruzalski, G.R.; Luck, C.F.

doi:10.1557/proc-210-569

Cited by 11 publications

(19 citation statements)

References 10 publications

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“…From Table , with an increase of Si/P ratio, the relative proportion of the NBO2 (Li + … − O–P) does not vary too much whereas NBO1 component (PO) decreases with BO (Si–O–P) component increase. The formation of heteroatom (Si–O–P) groups increases the network cross‐linking which facilitate Li + transfer between phosphate chains leading to higher mobility and ionic conductivity.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical properties and optical transmission of high Li⁺ conducting LiSiPON electrolyte films

Su¹,

Falgenhauer²,

Leichtweiß

et al. 2016

Physica Status Solidi (b)

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Lithium silicon phosphorus oxynitride (LiSiPON) thin films with different compositions have been prepared by RF magnetron sputtering in N2 by using three targets xLi2SiO3 · (1 − x) Li3PO4 with x = 0.1, 0.3, and 0.5. Compared with LiPON, the electrical properties of LiSiPON have been improved by introducing silicon. LiSiPON films deposited from the target 0.5Li2SiO3 · 0.5Li3PO4 yield the highest ionic conductivity of up to 9.7 × 10−6 S cm−1 with an activation energy of only 0.41 eV. The main mechanism for increasing ionic conductivity is the enhancement of carrier mobility. By DC polarization measurements the electronic partial conductivity was found at least seven orders of magnitude smaller than the ionic conductivity. Linear voltammetry results showed that the LiSiPON films are electrochemically stable in contact with stainless steel in the voltage range of 0–6 V. The substitution of silicon for phosphorus in the film evidenced from X‐ray photoelectron spectroscopy analysis indicated silicon in the film will create more abundant cross‐linking structures Si–O–P and (P, Si)–N < (P, Si), hence created more Li+ conducting paths which favored the higher mobility of lithium ions and larger ionic conductivity. The optical bandgap was found to decrease with increasing silicon content. We demonstrate that the prepared LiSiPON films with their larger ionic conductivity and low electronic conductivity may serve as an alternative to LiPON for applications in high energy density and high voltage lithium batteries.

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Section: Resultsmentioning

confidence: 99%

Electrochemical properties and optical transmission of high Li⁺ conducting LiSiPON electrolyte films

Su¹,

Falgenhauer²,

Leichtweiß

et al. 2016

Physica Status Solidi (b)

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“…Lithium phosphate based thin film electrolytes are generally deposited by sputtering, [4][5][6][7] pulsed laser deposition 8 and E-beam evaporation. 9 Because of shadow effects, these methods are hardly suitable for 3D deposition.…”

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Chemical Vapor Deposition of Lithium Phosphate Thin-Films for 3D All-Solid-State Li-Ion Batteries

Xie

Oudenhoven

Harks

et al. 2014

J. Electrochem. Soc.

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High quality Lithium phosphate (Li 3 PO 4 ) thin films have been deposited by metal-organic chemical vapor deposition (MOCVD), using tert-butyllithium and trimethyl phosphate as precursors. The Li 3 PO 4 films deposited at 300 • C yielded the highest ionic conductivity (3.9 × 10 −8 S · cm −1 ). Increasing the deposition temperature led to crystallization of the deposited films and, consequently, to lower ionic conductivities. Kinetic studies on planar substrates showed that Li 3 PO 4 deposition is a diffusion-controlled process in the temperature range of 300 to 500 • C. Li 3 PO 4 films have also been deposited on highly structured substrates to investigate, for the first time, the feasibility of 3D deposition of Li 3 PO 4 by MOCVD. Furthermore, very thin films of Li 3 PO 4 have been deposited onto thin film Si anodes and it was found that these layers effectively suppress the SEI formation and dramatically improve the cycle performance of Si film anodes. Driven by the fast development of autonomous devices, all-solidstate micro-batteries currently attract a lot of attention. The three dimensional (3D) all-solid-state Li-ion battery is a challenging concept, which will significantly improve the volumetric capacity and rate capability of micro-batteries.1-3 A stable thin film electrolyte is one of the important components for micro-batteries. Due to the relatively high Li-ion conductivity and (electro)chemical stability upon contact with Li anodes, 4 lithium phosphate thin films are among the most popularly used electrolytes for micro-batteries.Lithium phosphate based thin film electrolytes are generally deposited by sputtering, 4-7 pulsed laser deposition 8 and E-beam evaporation.9 Because of shadow effects, these methods are hardly suitable for 3D deposition. In addition, during the deposition process using these methods, there is a temperature difference between the substrate and the deposited films. The resulting thermal tensile stress may disadvantageously cause film cracking. 10Atomic layer deposition (ALD) and metal-organic chemical vapor deposition (MOCVD) are two methods that can deposit very homogeneous and conformal films on highly structured substrates. Unfortunately, the ALD method is relatively slow 11 and therefore rather unpractical for the deposition of battery materials. Several papers reported the chemical vapor deposition of nitrogen doped lithium phosphate 10,12 but none of these papers explored the feasibility of deposition in 3D. In this study, MOCVD is investigated to deposit Li 3 PO 4 thin films, using tert-butyllithium (t-BuLi) and trimethyl phosphate (TMPO) as precursors. The MOCVD process for Li 3 PO 4 thin film deposition has been developed and the influence of the substrate temperature on the morphology, crystal structure and ionic conductivity has been systematically studied. In order to investigate the feasibility of three dimensional deposition of Li 3 PO 4 by MOCVD, thin films were also deposited onto highly-structured substrates. The thickness development of the deposited thin f...

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“…The specific substrates, and especially the TiN films, show a nanocrystalline network, which influences very much the structure of the deposited LiNbO 3 films. Previous investigations indicated that such a deposition procedure give thin lithium niobate films of quite low resistivity and real fast relaxation time of the Liions, 5x10 -3 sec, similar to the ion relaxation time of the Lipon electrolyte [5,14].…”

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confidence: 86%

Influence of different substrates on the ionic conduction in LiCoO₂/LiNbO₃ thin‐film bi‐layers

Horopanitis

Perentzis

Papadimitriou

2008

Phys. Status Solidi (c)

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LiNbO3 thin films, deposited by e‐gun evaporation, show lithium deficiency, which is cured by “Li doping”. The “Li doping” of the films was achieved by preparing a structure of Li‐Nb‐O/Li/Li‐Nb‐O, which after annealing forms a homogenized LiNbO3 layer because of diffusion of Li in the two Li‐Nb‐O layers. The LiCoO2/LiNbO3 bi‐layers were prepared either on Stainless Steel/TiN or on Al2O3/Co/Pt substrates/ohmic‐contacts by depositing first either the cathode LiCoO2 or the electrolyte LiNbO3. The Nyquist plots of the AC impedance measurements of all structures showed that the interfaces prepared on Stainless‐Steel/TiN consisted of two semicircles. The structures deposited on Al2O3/Co/Pt showed a third semicircle, which is probably due to the roughness of the substrate. It is important that the ionic properties of the bi‐layers with the cathode material deposited first, a usual structure in a microbattery, are improved compared to the other structures. The quality of the LiNbO3 layer depends very much on the substrate. It can be evaluated from Arrhenius plots that the activation energy of this layer is considerably lower when the whole structure is deposited on Stainless Steel/TiN. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

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Thin Film Amorphous Electrolytes: The Li₂O-SiO₂-P₂O₅ System

Cited by 11 publications

References 10 publications

Electrochemical properties and optical transmission of high Li⁺ conducting LiSiPON electrolyte films

Electrochemical properties and optical transmission of high Li⁺ conducting LiSiPON electrolyte films

Chemical Vapor Deposition of Lithium Phosphate Thin-Films for 3D All-Solid-State Li-Ion Batteries

Influence of different substrates on the ionic conduction in LiCoO₂/LiNbO₃ thin‐film bi‐layers

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Thin Film Amorphous Electrolytes: The Li2O-SiO2-P2O5 System

Cited by 11 publications

References 10 publications

Electrochemical properties and optical transmission of high Li+ conducting LiSiPON electrolyte films

Electrochemical properties and optical transmission of high Li+ conducting LiSiPON electrolyte films

Chemical Vapor Deposition of Lithium Phosphate Thin-Films for 3D All-Solid-State Li-Ion Batteries

Influence of different substrates on the ionic conduction in LiCoO2/LiNbO3 thin‐film bi‐layers

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Thin Film Amorphous Electrolytes: The Li₂O-SiO₂-P₂O₅ System

Electrochemical properties and optical transmission of high Li⁺ conducting LiSiPON electrolyte films

Electrochemical properties and optical transmission of high Li⁺ conducting LiSiPON electrolyte films

Influence of different substrates on the ionic conduction in LiCoO₂/LiNbO₃ thin‐film bi‐layers