LiPON and NaPON glasses: A study of the ammonolysis of lithium and sodium metaphosphate melts

Souza, José Ezequiel de; Souza, Seila Rojas De; Gebhardt, Ryan; Kmiec, Steven; Whale, Alison; Martin, Steve W.

doi:10.1111/ijag.13508

Cited by 14 publications

(50 citation statements)

References 30 publications

(106 reference statements)

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“…Ammonolysis of Na 4 P 2 S 7-x O x Glasses. Ammonolysis of the Na 4 P 2 S 7-x O x glasses follows the methods used by De Souza et al 46 for the production of LiPON and NaPON bulk glasses. Due to the mass dependence on the N uptake into the melt, the sample size was held between 2.5 and 3.5 g for all experiments by controlling the geometry of the glass bars.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

“…Due to the mass dependence on the N uptake into the melt, the sample size was held between 2.5 and 3.5 g for all experiments by controlling the geometry of the glass bars. 46 The ammonolysis system is depicted in Figure S1 and is composed of a mullite tube furnace equipped with two watercooled end caps for N 2 and NH 3 gas inflow and exhaust. The exhaust port cap was equipped with a pushrod to move the sample during the experiment without atmospheric contamination.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

“…Reports by De Souza et al 46,52,59 have shown with Raman sspectroscopy that the N t species is the dominant form of nitrogen in both LiPON and NaPON glasses with N/P < 0.33. Significant concentrations of the N d species are only reported in glasses containing N/P > 0.33, where the preferential formation of N d over N t species is observed.…”

Section: Inorganicmentioning

confidence: 97%

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Synthesis, Short-Range Order Structure, and Thermal Properties of Mixed Oxy-sulfide Nitride (MOSN) Glasses

Kmiec

Martin

2021

Inorg. Chem.

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Nitrogen doping has been shown to greatly improve the stability of solid electrolyte (SE) materials at the anode and cathode interfaces in all solid-state batteries (ASSBs) as widely demonstrated by the LiPON family of compositions. In an effort to expand the use of nitrogen in SEs, in this study, mixed oxy-sulfide nitride (MOSN) glasses were prepared by direct ammonolysis of the sodium oxy-sulfide phosphate Na 4 P 2 S 7-x O x (NaPSO) glass series to understand the combined effects that oxygen and sulfur have on the incorporation of nitrogen. The short-range order (SRO) structures of the Na 4 P 2 S (7-x)-3/2yz O x-3/2y(1-z) N y (NaPSON) glasses were investigated with Raman and infrared (IR) spectroscopies to understand the effect that nitrogen has in the glass structure. The N content of the glasses was quantified by elemental analysis and confirmed through weight change measurements. By combining this information, it was further possible to determine the anion exchange ratio, z, for the N substitution of O and S as a function of the base NaPSO glass chemistry, x. The composition-dependent glass transition temperature, T g (x), measured with differential scanning calorimetry (DSC), was found to correlate well with the measured N/P ratio, y, in the NaPSON glasses.

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Section: ■ Experimental Methodsmentioning

confidence: 99%

Section: ■ Experimental Methodsmentioning

confidence: 99%

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Synthesis, Short-Range Order Structure, and Thermal Properties of Mixed Oxy-sulfide Nitride (MOSN) Glasses

Kmiec

Martin

2021

Inorg. Chem.

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“…For the large preform, the liquid was created as above and cast onto a preheated brass plate, covered with a second preheated brass plate, and then annealed at 290 °C overnight to form a rectangular preform approximately 10 cm by 25 cm by 1 cm. 40 After cooling, the preform was loaded into our custom-built thin film draw tower located inside of a N 2 glovebox (<0.1 ppm of O 2 and H 2 O). A schematic of the draw-tower is shown in Figure 1.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Electrochemical Behavior of Drawn Thin-Film Vitreous Lithium Metaphosphate

Wheaton

Kmiec

Schuler

et al. 2021

ACS Appl. Energy Mater.

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Lithium metaphosphate (LiPO3) thin-film glassy solid-state electrolyte (GSSE) ribbons with thicknesses varying from 35 to 800 μm have been drawn for the first time through softening and drawing of a cast and annealed preform of LiPO3 glass. The short-range order structure and composition of the thin-film glasses were confirmed to be identical to the bulk glass LiPO3 using Raman spectroscopy. Electrochemical impedance spectroscopy (EIS) was used to investigate the Li ionic conductivity of the thin-film GSSE samples and was essentially the same as that of the bulk LiPO3 glass. A model of area specific resistance (ASR) as a function of film thickness and temperature was generated and compared to resistances determined through equivalent circuit fitting of EIS generated Nyquist plots. The generated model compared well to the experimentally determined values. Symmetric cell cycling was conducted on the 50 μm thick samples to determine the cycling behavior and the durability of the electrolyte under applied voltage and sustained current. Evidence of the electrochemical stability of the LiPO3 thin-film GSSE against lithium metal was observed in the symmetric cell cycling as nearly perfectly flat and ohmic behavior cycling plateaus were found over a range of current densities. Prior to shorting, a critical current density of 65 μA/cm2 was obtained at 90 °C with a direct current (dc) Li ionic conductivity of 10–6.5 [Ω·cm]−1. While these current densities are low, this is the first report of a thin-film GSSE drawn into thicknesses of that required for high performance all-solid-state lithium batteries, and the proven stability and durability of this oxide GSSE is strong evidence that drawn thin-film GSSE materials, especially those with higher conductivities such as the well-studied sulfide glasses, are viable materials from which to create thin, easily processable solid-state electrolytes (SSEs) and warrant further research.

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“…This sort of segregation has also been suggested in view of the differences in rigidity between sodium and lithium oxynitride phosphates as studied by Paraschiv et al 6 The authors proposed that the smaller amount of PO 3 N groups detected in the LiPON glasses could cause a change in connectivity that produces variations in the structural rigidity of the network. Other authors as de Souza et al 13 have also attempted an evaluation of the glass homogeneity through a Raman analysis of their structure that permitted a reliable quantification of the chemical species involved and their evolution with the nitridation reaction. Nuclear magnetic resonance (NMR) spectroscopy has developed over the past decades as a key methodology to explore the structure of glasses on short and intermediate length scales.…”

Section: ■ Introductionmentioning

confidence: 99%

Structure and Dynamics of LiPON and NaPON Oxynitride Phosphate Glasses by Solid-State NMR

et al. 2021

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Oxynitride phosphate glasses are a subfield of phosphate-based glasses, where part of the oxygen of the network has been replaced by nitrogen, in a process commonly called nitridation, of the phosphate melt. Because of this, the properties of the glasses are greatly enhanced, notably mechanical and chemical resistance, which has resulted in an important field with applications in glass-to-metal sealing or as electrolytes for solidstate batteries when processed as thin films. Whereas the properties of oxynitride phosphates have been thoroughly researched in view of their prospected applications, the elucidation of their structure remains uncomplete in some aspects, notably in the way that the network building groups are interconnected as well as from the point of view of the role of the modifiers onto the nitrided network structure. In the present work, 1D, 2D, REDOR, and INADEQUATE NMR experiments have been complemented with high-temperature NMR of lithium and sodium oxynitride phosphate glasses to study the structural arrangement of the building units and its evolution with temperature. The results have evidenced that the network organization adopted by the glasses distinctively depends on the nature of the modifier cation. However, the results exclude any significant phase separation or segregation of oxide and oxynitride regions, despite some clustering of nitride species may be occurring, mostly in the lithiumcontaining glasses.

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LiPON and NaPON glasses: A study of the ammonolysis of lithium and sodium metaphosphate melts

Cited by 14 publications

References 30 publications

Synthesis, Short-Range Order Structure, and Thermal Properties of Mixed Oxy-sulfide Nitride (MOSN) Glasses

Synthesis, Short-Range Order Structure, and Thermal Properties of Mixed Oxy-sulfide Nitride (MOSN) Glasses

Electrochemical Behavior of Drawn Thin-Film Vitreous Lithium Metaphosphate

Structure and Dynamics of LiPON and NaPON Oxynitride Phosphate Glasses by Solid-State NMR

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