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7 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on Li3PS4 by Materials Project

Li3PS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four S2- atoms to form LiS4 tetrahedra that share corners with four equivalent LiS6 octahedra, corners with two equivalent PS4 tetrahedra, corners with four equivalent LiS4 tetrahedra, an edgeedge with one LiS6 octahedra, and an edgeedge with one PS4 tetrahedra. The corner-sharing octahedra tilt angles range from 18–54°. There are a spread of Li–S bond distances ranging from 2.46–2.49 Å. In the second Li1+ site, Li1+ is bonded to six S2- atoms to form distorted LiS6 octahedra that share corners with two equivalent PS4 tetrahedra, corners with eight equivalent LiS4 tetrahedra, edges with two equivalent LiS6 octahedra, edges with two equivalent LiS4 tetrahedra, and edges with two equivalent PS4 tetrahedra. There are a spread of Li–S bond distances ranging from 2.47–3.17 Å. P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share corners with two equivalent LiS6 octahedra, corners with four equivalent LiS4 tetrahedra, edges with two equivalent LiS6 octahedra, and edges with two equivalent LiS4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. There are a spread of P–S bond distances ranging from 2.04–2.10 Å. There are three inequivalent S2- sites. In the first S2- site, S2- is bonded in a 5-coordinate geometry to four Li1+ and one P5+ atom. In the second S2- site, S2- is bonded to four Li1+ and one P5+ atom to form distorted SLi4P trigonal bipyramids that share corners with two equivalent SLi4P trigonal bipyramids, corners with six equivalent SLi3P trigonal pyramids, and edges with two equivalent SLi3P trigonal pyramids. In the third S2- site, S2- is bonded to three Li1+ and one P5+ atom to form distorted SLi3P trigonal pyramids that share corners with three equivalent SLi4P trigonal bipyramids, corners with four equivalent SLi3P trigonal pyramids, and an edgeedge with one SLi4P trigonal bipyramid.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li3PS4 by Materials Project

Li3PS4 is Theoretical Carbon Structure-derived structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four S2- atoms to form LiS4 tetrahedra that share corners with four equivalent LiS4 tetrahedra, corners with four equivalent PS4 tetrahedra, corners with two equivalent LiS4 trigonal pyramids, and an edgeedge with one LiS4 trigonal pyramid. There are a spread of Li–S bond distances ranging from 2.38–2.50 Å. In the second Li1+ site, Li1+ is bonded to four S2- atoms to form LiS4 trigonal pyramids that share corners with four equivalent LiS4 tetrahedra, corners with four equivalent PS4 tetrahedra, and edges with two equivalent LiS4 tetrahedra. There are a spread of Li–S bond distances ranging from 2.41–2.60 Å. P5+ is bonded to four S2- atoms to form PS4 tetrahedra that share corners with eight equivalent LiS4 tetrahedra and corners with four equivalent LiS4 trigonal pyramids. There are a spread of P–S bond distances ranging from 2.05–2.07 Å. There are three inequivalent S2- sites. In the first S2- site, S2- is bonded to three Li1+ and one P5+ atom to form corner-sharing SLi3P tetrahedra. In the second S2- site, S2- is bonded to three Li1+ and one P5+ atom to form a mixture of edge and corner-sharing SLi3P tetrahedra. In the third S2- site, S2- is bonded to three Li1+ and one P5+ atom to form a mixture of edge and corner-sharing SLi3P trigonal pyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Wet-chemical synthesis of Li7P3S11 with tailored particle size for solid state electrolytes

The small-size solid-state electrodes (SSEs) with high Li+ conductivity play an important role in reducing the interfacial resistance between electrode materials and SSEs and defects between SSEs. As one of the most conductive sulfide based ionic conductors, scalable synthesis of Li7P3S11 with controllable particle sizes is highly desired but rarely reported. Here, we report a facile wet-chemical synthesis method to prepare Li7P3S11 SSEs with variable sizes for all-solid-state lithium batteries (ASSLBs). By fully dissolving 70Li2S-30P2S5 precursors in ethyl acetate solution, the particle size of Li7P3S11 can be manipulated into as small as ~110 nm and high Li+ conductivity of 1.05 mS cm-1 can be achieved. A systematical mechanistic study of solvent effects suggests that the controlled particle sizes are attributed to the excellent solvability and low binding energy of ethyl acetate solvent toward solutes. Moreover, this generic method can be extended to the facilely synthesis of Li3PS4 nanoparticles with an average size of ~200 nm and high Li+ conductivity of 0.1 mS cm-1.

Zhou, Jianbin↗
DOE OSTI2020

In Situ Investigation of Chemomechanical Effects in Thiophosphate Solid Electrolytes

Solid-state batteries can suffer from catastrophic failure at high current densities due to solid electrolyte fracture, interface decomposition, or lithium filament growth. Failure is linked to chemomechanical material transformations that can manifest during electrochemical cycling. We systematically investigate how solid electrolyte microstructure and interfacial decomposition (e.g., interphase) affect failure mechanisms in lithium thiophosphates (Li3PS4, LPS) electrolytes. Kinetically metastable interphases are engineered with iodine doping, and microstructural control is achieved using milling and annealing processing techniques. In situ transmission electron microscopy reveals iodine diffusion to the interphase, and upon electrochemical cycling, pores are formed in the interphase region. In situ synchrotron tomography reveals that interphase pore formation drives edge fracture events, which are the origin of through-plane fracture failure. Fractures in thiophosphate electrolytes actively grow toward regions of higher porosity and are affected by heterogeneity in microstructure (e.g., porosity factor). This report provides fundamental design guidelines for high-performance solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Non-Conductive Polymers Enable Higher Ionic Conductivities and Suppress Reactivity in Hybrid Sulfide-Polymer Solid State Electrolytes

Hybrid ceramic-polymer solid state electrolytes are promising candidates to enable energy-dense lithium metal batteries by leveraging inorganic high ionic conductivity and flexible polymer mechanical properties. However, studies of hybrid electrolytes using sulfide-type inorganics such as Li3PS4 (LPS) have largely focused on combining the inorganic with commercial poly(ethylene oxide) (PEO). PEO has proven to be insufficient for use in hybrid systems because it reacts with LPS and provides a competing pathway for ion transport, therefore producing a hybrid with low conductivity. Our work shows that using nonconductive, nonpolar polyethylene (PE) in a hybrid electrolyte with LPS eliminates both polymer and inorganic degradation and remarkably exhibit higher conductivities than those containing PEO at different polymer and salt concentrations. Using tracer-exchange NMR, we observe that the nonconductive nature of PE allows for iontransport through the inorganic whereas PEO provides a separate, competing pathway for lithium transport. Furthermore, compared to pure LPS, these hybrids enable longer term lithium cycling at 60°C. Our work shows that the path to enabling conductive and stable sulfide hybrids for solid state lithium metal batteries may be through the use of nonconductive, nonreactive polymers.

batteries↗
DOE OSTI2020

Low-temperature paddlewheel effect in glassy solid electrolytes

Glasses are promising electrolytes for use in solid-state batteries. Nevertheless, due to their amorphous structure, the mechanisms that underlie their ionic conductivity remain poorly understood. Here, ab initio molecular dynamics is used to characterize migration processes in the prototype glass, 75Li2S–25P2S5. Lithium migration occurs via a mechanism that combines concerted motion of lithium ions with large, quasi-permanent reorientations of PS4 3- anions. This latter effect, known as the ‘paddlewheel’ mechanism, is typically observed in high temperature crystalline polymorphs. In contrast to the behavior of crystalline materials, in the glass paddlewheel dynamics contribute to Lithium-ion mobility at room temperature. Paddlewheel contributions are confirmed by characterizing spatial, temporal, vibrational, and energetic correlations with Lithium motion. Furthermore, the dynamics in the glass differ from those in the stable crystalline analogue, γ-Li3PS4, where anion reorientations are negligible and ion mobility is reduced. These data imply that glasses containing complex anions, and in which covalent network formation is minimized, may exhibit paddlewheel dynamics at low temperature. Consequently, these systems may be fertile ground in the search for new solid electrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nonuniform Ionic and Electronic Transport of Ceramic and Polymer/Ceramic Hybrid Electrolyte by Nanometer-Scale Operando Imaging for Solid-State Battery

Replacing the liquid electrolyte in lithium batteries with solid-state ion conductor is promising for next-generation energy storage that is safe and has high energy density. In this work, nanometer-resolution ionic and electronic transport imaging of Li 3 PS 4 (LPS), a solid-state electrolyte (SSE), is reported. This nm resolution is achieved by using a logarithm-scale current amplifier that enhances the current sensitivity to the fA range. Large fluctuations of ion current—one to two orders of magnitude on the LPS and on the LPS region of a polymer/LPS bulk hybrid SSE—that must be mitigated to eliminate Li dendrite formation and growth, are found. This ion current fluctuation is understood in terms of highly anisotropic transport kinetic barriers along the different crystalline axes due to different grain orientations in the polycrystalline and glass ceramic materials. The results on the bulk hybrid SSE show a sharp transition of ionic and electronic transport at the LPS/polymer boundary and decreases in average ionic current with decreasing polyimine particle size and with extensive cycling. The results elucidate the mechanism of polyimine extension into interparticles to prevent Li dendrite growth. This work opens up novel characterization of charge transport, which relates to Li plating and stripping for solid-state-batteries.

Li3PS4↗