Abstract
Here, we provide an in-depth structural characterization of the amorphous ionic glasses LiPON and LiSiPON with high Li content. Based on ab initio molecular dynamics simulations, the structure of these materials is an inverted structure with either isolated polyanion tetrahedra or polyanion dimers in a Li+ matrix. Based on neutron scattering data, this type of inverted structure leads to a significant amount of medium-range ordering in the structure, as demonstrated by two sharp diffraction peaks and a periodic structural oscillation in the density function G(r). While this medium-range ordering is commonly observed in liquids and metallic glasses, it has not previously been observed in oxides. On a local scale, adding N and Si increases the number of anion bridges and polyanion dimer structures, leading to higher ionic conductivity. In the medium-range ordering, the addition of Si leads to more disorder in the polyanion substructure but a significant increase in the ordering of the O substructure. Finally, we demonstrate that this inverted structure with medium-range ordering results in a glassy material that is both mechanically stiff and ductile on the nanoscale.
| Original language | English |
|---|---|
| Pages (from-to) | 2730-2739 |
| Number of pages | 10 |
| Journal | Chemistry of Materials |
| Volume | 35 |
| Issue number | 7 |
| DOIs | |
| State | Published - Apr 11 2023 |
Funding
The authors would like to acknowledge the support of Paul Albertus at ARPA-E and Michael Naguib who helped with initial materials synthesis. Funding for this work was primarily provided by ARPA-E Award # 00000775. M.K. and B.K. were also partially supported by Robert Bosch LLC. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. T.E. was supported by the U. S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. V.T. and S.W.M were supported in part by the NSF grant number 1936913 and by DOE contract number DE-EE0008852. This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). Support for Neutron scattering experiments was provided through a Spallation Neutron Source User Proposal IPTS 19271.1. The authors would like to acknowledge the support of Paul Albertus at ARPA-E and Michael Naguib who helped with initial materials synthesis. Funding for this work was primarily provided by ARPA-E Award # 00000775. M.K. and B.K. were also partially supported by Robert Bosch LLC. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. T.E. was supported by the U. S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. V.T. and S.W.M were supported in part by the NSF grant number 1936913 and by DOE contract number DE-EE0008852. This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Support for Neutron scattering experiments was provided through a Spallation Neutron Source User Proposal IPTS 19271.1.
| Funders | Funder number |
|---|---|
| DOE Public Access Plan | |
| National Science Foundation | 1936913 |
| U.S. Department of Energy | DE-AC05-00OR22725, DE-EE0008852 |
| Office of Science | |
| Advanced Research Projects Agency - Energy | 00000775 |
| Basic Energy Sciences | |
| Oak Ridge National Laboratory | |
| Robert Bosch | |
| Division of Materials Sciences and Engineering |
