TY - JOUR
T1 - High Li+ and Na+ Conductivity in New Hybrid Solid Electrolytes based on the Porous MIL-121 Metal Organic Framework
AU - Zettl, Roman
AU - Lunghammer, Sarah
AU - Gadermaier, Bernhard
AU - Boulaoued, Athmane
AU - Johansson, Patrik
AU - Wilkening, H. Martin R.
AU - Hanzu, Ilie
PY - 2021
Y1 - 2021
N2 - Solid-state electrolytes (SSEs) can leapfrog the development of all-solid-state batteries (ASSBs), enabling them to power electric vehicles and to store renewable energy from intermittent sources. Here, a new hybrid Li+ and Na+ conducting SSE based on the MIL-121 metal-organic framework (MOF) structure is reported. Following synthesis and activation of the MOF, the free carboxylic units along the 1D pores are functionalized with Li+ or Na+ ions by ion exchange. Ion dynamics are investigated by broadband impedance spectroscopy and by 7Li and 23Na NMR spin-lattice relaxation. A crossover at 50 °C (Li+) and at 10 °C (Na+) from correlated to almost uncorrelated motion at higher temperature is observed, which is in line with Ngai's coupling model. Alternatively, in accordance to the jump relaxation model of Funke, at low temperature only a fraction of the jump processes are successful as lattice rearrangement in the direct vicinity of Li+ (Na+) is slow. 1H NMR unambiguously shows that Li+ is the main charge carrier. Conductivities reach 0.1 mS cm−1 (298 K, Na+) while the activation energies are 0.28 eV (Li+) and 0.36 eV (Na+). The findings pave the way towards development of easily tunable and rationally adjustable high-performance MOF-based hybrid SSEs for ASSBs.
AB - Solid-state electrolytes (SSEs) can leapfrog the development of all-solid-state batteries (ASSBs), enabling them to power electric vehicles and to store renewable energy from intermittent sources. Here, a new hybrid Li+ and Na+ conducting SSE based on the MIL-121 metal-organic framework (MOF) structure is reported. Following synthesis and activation of the MOF, the free carboxylic units along the 1D pores are functionalized with Li+ or Na+ ions by ion exchange. Ion dynamics are investigated by broadband impedance spectroscopy and by 7Li and 23Na NMR spin-lattice relaxation. A crossover at 50 °C (Li+) and at 10 °C (Na+) from correlated to almost uncorrelated motion at higher temperature is observed, which is in line with Ngai's coupling model. Alternatively, in accordance to the jump relaxation model of Funke, at low temperature only a fraction of the jump processes are successful as lattice rearrangement in the direct vicinity of Li+ (Na+) is slow. 1H NMR unambiguously shows that Li+ is the main charge carrier. Conductivities reach 0.1 mS cm−1 (298 K, Na+) while the activation energies are 0.28 eV (Li+) and 0.36 eV (Na+). The findings pave the way towards development of easily tunable and rationally adjustable high-performance MOF-based hybrid SSEs for ASSBs.
KW - conductivity spectroscopy
KW - ion dynamics
KW - lithium ion conductors
KW - metal–organic frameworks
KW - sodium ion conductors
KW - solid-state batteries
UR - http://www.scopus.com/inward/record.url?scp=85101559120&partnerID=8YFLogxK
U2 - 10.1002/aenm.202003542
DO - 10.1002/aenm.202003542
M3 - Article
AN - SCOPUS:85101559120
SN - 1614-6832
VL - 11
JO - Advanced Energy Materials
JF - Advanced Energy Materials
IS - 16
M1 - 2003542
ER -