The Li–Si–(O)–N system revisited: Structural characterization of Li21Si3N11 and Li7SiN3O

Casas‐Cabañas, Montse; Santner, Heinrich

doi:10.1016/j.jssc.2014.02.022

Cited by 7 publications

(9 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Bragg diffraction patterns were acquired at the I15–1 beamline at Diamond Light Source (76 keV beam energy) using a 2D detector (PerkinElmer XRD 1611 CP3). Initial processing was conducted using the Gudrun software, while fitting of PDF data was conducted using the PDFgui software and was refined based on published structural data of the relevant phases: c-Si, graphite, LiC 6 , LiC 12 , α-Si 3 N 4 , c-Li 3 N, c-LiSi 2 N 3 , c-Li 2 SiN 2 , c-Li 7 Si 3 , c-Li 13 Si 4 , and c-Li 15 Si 4 . No attempt was made to subtract the PDF signal from the carbon-containing species, which were rather fit as parts of the sample.…”

Section: Methodsmentioning

confidence: 99%

Stoichiometry-Controlled Reversible Lithiation Capacity in Nanostructured Silicon Nitrides Enabled by in Situ Conversion Reaction

et al. 2021

View full text Add to dashboard Cite

In modern Li-based batteries, alloying anode materials have the potential to drastically improve the volumetric and specific energy storage capacity. For the past decade silicon has been viewed as a “Holy Grail” among these materials; however, severe stability issues limit its potential. Herein, we present amorphous substoichiometric silicon nitride (SiN x ) as a convertible anode material, which allows overcoming the stability challenges associated with common alloying materials. Such material can be synthesized in a form of nanoparticles with seamlessly tunable chemical composition and particle size and, therefore, be used for the preparation of anodes for Li-based batteries directly through conventional slurry processing. Such SiN x materials were found to be capable of delivering high capacity that is controlled by the initial chemical composition of the nanoparticles. They exhibit an exceptional cycling stability, largely maintaining structural integrity of the nanoparticles and the complete electrodes, thus delivering stable electrochemical performance over the course of 1000 charge/discharge cycles. Such stability is achieved through the in situ conversion reaction, which was herein unambiguously confirmed by pair distribution function analysis of cycled SiN x nanoparticles revealing that active silicon domains and a stabilizing Li2SiN2 phase are formed in situ during the initial lithiation.

show abstract

Section: Methodsmentioning

confidence: 99%

Stoichiometry-Controlled Reversible Lithiation Capacity in Nanostructured Silicon Nitrides Enabled by in Situ Conversion Reaction

et al. 2021

View full text Add to dashboard Cite

show abstract

“…The exact methodology can be found in the experimental section. Equation (2) shows the originally expected reaction with the formation of Li 5 SiNO 3 mentioned by Podsiadło but not structurally described. [5] SiO…”

Section: Resultsmentioning

confidence: 81%

“…In fact, Li 4 Si 0.8 N 2.4 (Li 2 O) 1.6 found by Juza et al as well as Li 7 SiN 3 O described much later by Casas-Cabanas et al match these requirements. [1,2] Details of all known members of this series can be found in Table 1. However, both compounds mentioned above were analyzed only by powder X-ray diffraction.…”

Section: Introductionmentioning

confidence: 99%

An Unexpected New Member of the Family of Lithium Oxonitridosilicates – Li₇Si₂NO₆

et al. 2023

View full text Add to dashboard Cite

With Li7Si2NO6, a new member of the family of lithium oxonitridosilicates with a so far unseen structure type could be synthesized. Using a high‐temperature solid‐state reaction in open nickel crucibles under nitrogen flow, it was possible to obtain single crystals from the starting materials SiO2, Li3N, and Li2O at temperatures of 900 °C. Single crystal X‐ray diffraction data yielded lattice parameters of a=5.0934(2), b=7.4128(2), c=8.5918(2) Å, α=75.16(1)°, β=87.36(1)°, γ=73.01(1)° and a cell volume of V=299.75(2) Å3. The compound, crystallizing in the triclinic space group P (no. 2), consists of a highly condensed anionic network built up by [SiNO3]‐, [LiO4]‐, and [LiN2O2]‐tetrahedra as well as lithium in octahedral coordination as completing cation. With an activation barrier of 695 meV for lithium migration, Li7Si2NO6 is a potential lithium‐ion conductor. The structure allows a classification not only as a sorosilicate but also as a tecto‐lithosilicate and most precisely as a lithium oxonitridolithosilicate, when the different coordinations of the lithium ions are taken into account. Interestingly, the new compound is none of the several proposed representatives of the lithium oxonitridosilicates, thus expanding this substance class unexpectedly.

show abstract

“…The Si−N tetrahedron will be distorted but still preserve the bonding topology that Si is coordinated with four nitrogen atoms; otherwise, it is called "no enough valence of Si" such as BaSi 6 N 8 and SrSi 6 N 8 , which are not included in our statistics to avoid ambiguity. Re 7 Si 6 N 15 (Re = La, Ce, Pr) 28 with superstructure, Li 5 SiN 3 33 and Li 21 Si 3 N 11 34 with sharing Li and Si crystallographic site, Li 8 SiN 4 34 with unresolved structure, and compounds synthesized only at high pressure or stabilized only at high temperature are also excluded in statistics.…”

Section: ■ the Change Of Chemical Bondmentioning

confidence: 99%

The Inductive Effect in Nitridosilicates and Oxysilicates and Its Effects on 5d Energy Levels of Ce³⁺

et al. 2018

View full text Add to dashboard Cite

The inductive effect exists widely in inorganic compounds and accounts well for many physicochemical properties. However, until now this effect has not been characterized quantitatively. In this work, we collected and analyzed the structural data of more than 100 nitridosilicates and oxysilicates, whose structures typically consist of [SiN] or [SiO] tetrahedra. We introduce a new parameter, the inductive effect factor μΔχ, related to the difference of electronegativity between constituent metal elements and silicon. Then, a linear relationship is established between average length of Si-N/Si-O bonds and the inductive factor with the help of statistical method, that is, l̅ = 1.7313 + 0.0166 μΔχ (Å) with adjusted (adj) R = 0.800 for Si-N and l̅ = 1.6221 + 0.0035 μΔχ(Å) with adj R = 0.240 for Si-O. Furthermore, our research shows that the distinct positive correlation does exist between the inductive factor and the centroid shift of 5d levels of Ce. This work will help us understanding the inductive effect deeply and quantitatively.

show abstract

The Li–Si–(O)–N system revisited: Structural characterization of Li21Si3N11 and Li7SiN3O

Cited by 7 publications

References 41 publications

Stoichiometry-Controlled Reversible Lithiation Capacity in Nanostructured Silicon Nitrides Enabled by in Situ Conversion Reaction

Stoichiometry-Controlled Reversible Lithiation Capacity in Nanostructured Silicon Nitrides Enabled by in Situ Conversion Reaction

An Unexpected New Member of the Family of Lithium Oxonitridosilicates – Li₇Si₂NO₆

The Inductive Effect in Nitridosilicates and Oxysilicates and Its Effects on 5d Energy Levels of Ce³⁺

Contact Info

Product

Resources

About

The Li–Si–(O)–N system revisited: Structural characterization of Li21Si3N11 and Li7SiN3O

Cited by 7 publications

References 41 publications

Stoichiometry-Controlled Reversible Lithiation Capacity in Nanostructured Silicon Nitrides Enabled by in Situ Conversion Reaction

Stoichiometry-Controlled Reversible Lithiation Capacity in Nanostructured Silicon Nitrides Enabled by in Situ Conversion Reaction

An Unexpected New Member of the Family of Lithium Oxonitridosilicates – Li7Si2NO6

The Inductive Effect in Nitridosilicates and Oxysilicates and Its Effects on 5d Energy Levels of Ce3+

Contact Info

Product

Resources

About

An Unexpected New Member of the Family of Lithium Oxonitridosilicates – Li₇Si₂NO₆

The Inductive Effect in Nitridosilicates and Oxysilicates and Its Effects on 5d Energy Levels of Ce³⁺