NASICON LiM2(PO4)3 electrolyte (M=Zr) and electrode (M=Ti) materials for all solid-state Li-ion batteries with high total conductivity and low interfacial resistance

Hany El-Shinawi, Anna Regoutz, David J. Payne, Edmund J. Cussen, Serena A. Corr

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

All solid-state batteries based on NASICON-type LiM2(PO4)3 electrolyte phases are highly promising owing to their high ionic conductivities and chemical stabilities. Unlike Ti-based phases, extensively studied as Li+ solid electrolyte membranes, LiZr2(PO4)3 (LZP) is expected to form a stable interface with a metallic lithium anode, a challenge which has posed a serious roadblock to realising safe all solid-state batteries. However, prohibitively large grain boundary resistances are often observed in this material and this issue, combined with processing difficulties in fabricating LZP in dense forms, has impinged on the application of LZP as a solid electrolyte for all solid-state batteries. To overcome these shortcomings and demonstrate the excellent potential of LZP as a solid electrolyte, we have developed a simple approach, based on sol-gel chemistry, to effectively improve the densification of the material leading to higher total conductivity than previously reported (1.0 × 10-4 S cm-1 at 80 °C) and enabling the investigation of the material as a Li+ solid electrolyte without the need for elaborate post-processing steps. The interfacial resistance decreases dramatically on using thin layers of Au buffer to improve the contact between Li and the LZP surface. The Li/LZP interface shows constant resistance upon Li+ cycling (at 40 µA/Cm2), despite the formation of a passivation layer of Li3P/Li8ZrO6 on the LZP surface. This is consistent with the prediction that this surface layer serves as a Li+ conductive, solid electrolyte interface between Li and LZP. Finally, an analogue material, LiTi2(PO4)3, is also introduced and demonstrated as an electrode material for proposed LZP-based all-solid-state batteries.
LanguageEnglish
Number of pages8
JournalJournal of Materials Chemistry. A
Early online date23 Jan 2018
DOIs
Publication statusPublished - 7 Apr 2018

Fingerprint

Solid electrolytes
Electrolytes
Electrodes
Chemical stability
Ionic conductivity
Processing
Densification
Lithium
Passivation
Sol-gels
Buffers
Anodes
Grain boundaries
Lithium-ion batteries
Membranes

Keywords

  • lithium battery
  • solid electrolytes
  • solid state battery

Cite this

@article{a533578919fa40e1898660a021a2945b,
title = "NASICON LiM2(PO4)3 electrolyte (M=Zr) and electrode (M=Ti) materials for all solid-state Li-ion batteries with high total conductivity and low interfacial resistance",
abstract = "All solid-state batteries based on NASICON-type LiM2(PO4)3 electrolyte phases are highly promising owing to their high ionic conductivities and chemical stabilities. Unlike Ti-based phases, extensively studied as Li+ solid electrolyte membranes, LiZr2(PO4)3 (LZP) is expected to form a stable interface with a metallic lithium anode, a challenge which has posed a serious roadblock to realising safe all solid-state batteries. However, prohibitively large grain boundary resistances are often observed in this material and this issue, combined with processing difficulties in fabricating LZP in dense forms, has impinged on the application of LZP as a solid electrolyte for all solid-state batteries. To overcome these shortcomings and demonstrate the excellent potential of LZP as a solid electrolyte, we have developed a simple approach, based on sol-gel chemistry, to effectively improve the densification of the material leading to higher total conductivity than previously reported (1.0 × 10-4 S cm-1 at 80 °C) and enabling the investigation of the material as a Li+ solid electrolyte without the need for elaborate post-processing steps. The interfacial resistance decreases dramatically on using thin layers of Au buffer to improve the contact between Li and the LZP surface. The Li/LZP interface shows constant resistance upon Li+ cycling (at 40 µA/Cm2), despite the formation of a passivation layer of Li3P/Li8ZrO6 on the LZP surface. This is consistent with the prediction that this surface layer serves as a Li+ conductive, solid electrolyte interface between Li and LZP. Finally, an analogue material, LiTi2(PO4)3, is also introduced and demonstrated as an electrode material for proposed LZP-based all-solid-state batteries.",
keywords = "lithium battery , solid electrolytes, solid state battery",
author = "Hany El-Shinawi and Anna Regoutz and Payne, {David J.} and Cussen, {Edmund J.} and Corr, {Serena A.}",
year = "2018",
month = "4",
day = "7",
doi = "10.1039/C7TA08715B",
language = "English",
journal = "Journal of Materials Chemistry. A",
issn = "2050-7488",

}

NASICON LiM2(PO4)3 electrolyte (M=Zr) and electrode (M=Ti) materials for all solid-state Li-ion batteries with high total conductivity and low interfacial resistance. / El-Shinawi, Hany; Regoutz, Anna; Payne, David J.; Cussen, Edmund J.; Corr, Serena A.

In: Journal of Materials Chemistry. A , 07.04.2018.

Research output: Contribution to journalArticle

TY - JOUR

T1 - NASICON LiM2(PO4)3 electrolyte (M=Zr) and electrode (M=Ti) materials for all solid-state Li-ion batteries with high total conductivity and low interfacial resistance

AU - El-Shinawi, Hany

AU - Regoutz, Anna

AU - Payne, David J.

AU - Cussen, Edmund J.

AU - Corr, Serena A.

PY - 2018/4/7

Y1 - 2018/4/7

N2 - All solid-state batteries based on NASICON-type LiM2(PO4)3 electrolyte phases are highly promising owing to their high ionic conductivities and chemical stabilities. Unlike Ti-based phases, extensively studied as Li+ solid electrolyte membranes, LiZr2(PO4)3 (LZP) is expected to form a stable interface with a metallic lithium anode, a challenge which has posed a serious roadblock to realising safe all solid-state batteries. However, prohibitively large grain boundary resistances are often observed in this material and this issue, combined with processing difficulties in fabricating LZP in dense forms, has impinged on the application of LZP as a solid electrolyte for all solid-state batteries. To overcome these shortcomings and demonstrate the excellent potential of LZP as a solid electrolyte, we have developed a simple approach, based on sol-gel chemistry, to effectively improve the densification of the material leading to higher total conductivity than previously reported (1.0 × 10-4 S cm-1 at 80 °C) and enabling the investigation of the material as a Li+ solid electrolyte without the need for elaborate post-processing steps. The interfacial resistance decreases dramatically on using thin layers of Au buffer to improve the contact between Li and the LZP surface. The Li/LZP interface shows constant resistance upon Li+ cycling (at 40 µA/Cm2), despite the formation of a passivation layer of Li3P/Li8ZrO6 on the LZP surface. This is consistent with the prediction that this surface layer serves as a Li+ conductive, solid electrolyte interface between Li and LZP. Finally, an analogue material, LiTi2(PO4)3, is also introduced and demonstrated as an electrode material for proposed LZP-based all-solid-state batteries.

AB - All solid-state batteries based on NASICON-type LiM2(PO4)3 electrolyte phases are highly promising owing to their high ionic conductivities and chemical stabilities. Unlike Ti-based phases, extensively studied as Li+ solid electrolyte membranes, LiZr2(PO4)3 (LZP) is expected to form a stable interface with a metallic lithium anode, a challenge which has posed a serious roadblock to realising safe all solid-state batteries. However, prohibitively large grain boundary resistances are often observed in this material and this issue, combined with processing difficulties in fabricating LZP in dense forms, has impinged on the application of LZP as a solid electrolyte for all solid-state batteries. To overcome these shortcomings and demonstrate the excellent potential of LZP as a solid electrolyte, we have developed a simple approach, based on sol-gel chemistry, to effectively improve the densification of the material leading to higher total conductivity than previously reported (1.0 × 10-4 S cm-1 at 80 °C) and enabling the investigation of the material as a Li+ solid electrolyte without the need for elaborate post-processing steps. The interfacial resistance decreases dramatically on using thin layers of Au buffer to improve the contact between Li and the LZP surface. The Li/LZP interface shows constant resistance upon Li+ cycling (at 40 µA/Cm2), despite the formation of a passivation layer of Li3P/Li8ZrO6 on the LZP surface. This is consistent with the prediction that this surface layer serves as a Li+ conductive, solid electrolyte interface between Li and LZP. Finally, an analogue material, LiTi2(PO4)3, is also introduced and demonstrated as an electrode material for proposed LZP-based all-solid-state batteries.

KW - lithium battery

KW - solid electrolytes

KW - solid state battery

UR - http://pubs.rsc.org/en/journals/journalissues/ta#!recentarticles

U2 - 10.1039/C7TA08715B

DO - 10.1039/C7TA08715B

M3 - Article

JO - Journal of Materials Chemistry. A

T2 - Journal of Materials Chemistry. A

JF - Journal of Materials Chemistry. A

SN - 2050-7488

ER -