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@ARTICLE{Taoussi:1046447,
author = {Taoussi, S. and Ouaha, A. and Naji, M. and Hoummada, K. and
Lahmar, A. and Manoun, B. and Campos, A. and Stocker, P. and
frielinghaus, H. and El bouari, A. and Zhang, Y. and Bih,
L.},
title = {{N}ovel {M}n2+-doped {NASICON} glass-ceramic electrolyte
with engineered columnar microstructure for high lithium-ion
conductivity},
journal = {Journal of power sources},
volume = {658},
issn = {0378-7753},
address = {New York, NY [u.a.]},
publisher = {Elsevier},
reportid = {FZJ-2025-03804},
pages = {238266},
year = {2025},
abstract = {Glass-ceramic electrolytes are poised to revolutionize
energy storage as breakthrough candidates for
next-generation all-solid-state lithium batteries. This
study introduces a high-performance and new Mn-doped
NASICON-type (Li1.2Mn0.1Ti1.9(PO4)3) phase within a
glass-ceramic electrolyte, synthesized via a melt-quenching
and crystallization protocol. Crystallization analysis
reveals a surface-to-bulk phase transformation via a
one-dimensional nucleation process, with a low activation
energy of 161.68 kJ.mol-1, enabling a Li-enriched NASICON
matrix at reduced temperatures. Structural characterization
through Rietveld-refined XRD, and 7Li and 31P MAS NMR
spectroscopy, verified Mn2+ substitution within the crystal
lattice, causing bottleneck size expansion and weakened
Li+-O bonding, enhancing ion mobility. FT-IR and Raman
spectra further confirm the successful formation of the
Li-rich NASICON phase. SEM/TEM imaging revealed a unique
columnar grain morphology that reduces grain boundary areas
and porosity, while the residual glass phase $(11.2\%)$
enhances interfacial Li⁺ transfer. The optimized LMnTP-0GC
composition (30Li2O-20TiO2-20MnO-30P2O5) delivered
high-ionic conductivity (2.73×10-4 S.cm-1at RT), low
electronic leakage (3.425×10-8 S.cm-1), and near-unity
Li⁺ transference number (0.9998) outperforming undoped
LiTi2(PO4)3 and Mn-enriched counterparts. The
Li|LMnTP-0GC|Li cell achieves 2 mA.cm-2 CCD and stable
cycling for 200 h, while the Li|LMnTP-0GC|LFP cell delivers
130.00 mAh.g-1 with $96.40\%$ retention after 50 cycles at
0.1C.},
cin = {JCNS-FRM-II / MLZ / JCNS-4},
ddc = {620},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 / I:(DE-588b)4597118-3 /
I:(DE-Juel1)JCNS-4-20201012},
pnm = {6G4 - Jülich Centre for Neutron Research (JCNS) (FZJ)
(POF4-6G4) / 632 - Materials – Quantum, Complex and
Functional Materials (POF4-632)},
pid = {G:(DE-HGF)POF4-6G4 / G:(DE-HGF)POF4-632},
experiment = {EXP:(DE-MLZ)NOSPEC-20140101},
typ = {PUB:(DE-HGF)16},
doi = {10.1016/j.jpowsour.2025.238266},
url = {https://juser.fz-juelich.de/record/1046447},
}