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Extended condensed ultraphosphate frameworks with monovalent ions combine lithium mobility with high computed electrochemical stability

DOI: 10.1021/jacs.1c07874 DOI Help

Authors: Guopeng Han (University of Liverpool) , Andrij Vasylenko (University of Liverpool) , Alex R. Neale (University of Liverpool) , Benjamin B. Duff (University of Liverpool) , Ruiyong Chen (University of Liverpool) , Matthew S. Dyer (University of Liverpool) , Yun Dang (University of Liverpool) , Luke Daniels (University of Liverpool) , Marco Zanella (University of Liverpool) , Craig Robertson (University of Liverpool) , Laurence J. Kershaw Cook (University of Liverpool) , Anna-Lena Hansen (Karlsruhe Institute of Technology) , Michael Knapp (Karlsruhe Institute of Technology) , Laurence J. Hardwick (University of Liverpool) , Frédéric Blanc (University of Liverpool) , John B. Claridge (University of Liverpool) , Matthew J. Rosseinsky (University of Liverpool)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society , VOL 306

State: Published (Approved)
Published: October 2021
Diamond Proposal Number(s): 21726

Open Access Open Access

Abstract: Extended anionic frameworks based on condensation of polyhedral main group non-metal anions offer a wide range of structure types. Despite the widespread chemistry and earth abundance of phosphates and silicates, there are no reports of extended ultraphosphate anions with lithium. We describe the lithium ultraphosphates Li3P5O14 and Li4P6O17 based on extended layers and chains of phosphate, respectively. Li3P5O14 presents a complex structure containing infinite ultraphosphate layers with 12-membered rings that are stacked alternately with lithium polyhedral layers. Two distinct vacant tetrahedral sites were identified at the end of two distinct finite Li6O1626– chains. Li4P6O17 features a new type of loop-branched chain defined by six PO43– tetrahedra. The ionic conductivities and electrochemical properties of Li3P5O14 were examined by impedance spectroscopy combined with DC polarization, NMR spectroscopy, and galvanostatic plating/stripping measurements. The structure of Li3P5O14 enables three-dimensional lithium migration that affords the highest ionic conductivity (8.5(5) × 10–7 S cm–1 at room temperature for bulk), comparable to that of commercialized LiPON glass thin film electrolytes, and lowest activation energy (0.43(7) eV) among all reported ternary Li–P–O phases. Both new lithium ultraphosphates are predicted to have high thermodynamic stability against oxidation, especially Li3P5O14, which is predicted to be stable to 4.8 V, significantly higher than that of LiPON and other solid electrolytes. The condensed phosphate units defining these ultraphosphate structures offer a new route to optimize the interplay of conductivity and electrochemical stability required, for example, in cathode coatings for lithium ion batteries.

Journal Keywords: Anions; Crystal structure; Layers; Phosphates; Lithium

Diamond Keywords: Batteries; Lithium-ion

Subject Areas: Materials, Chemistry, Energy

Instruments: I19-Small Molecule Single Crystal Diffraction

Other Facilities: P02.1 at PETRA III

Added On: 25/10/2021 08:22


Discipline Tags:

Physical Chemistry Energy Energy Storage Materials Science Energy Materials Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)