Transferring lithium ions in the nanochannels of flexible metal-organic frameworks featuring superchaotropic metallacarborane guests: mechanism of ionic conductivity at atomic resolution

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F20%3A00533405" target="_blank" >RIV/61389013:_____/20:00533405 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/68378271:_____/20:00533405

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acsami.0c12293" target="_blank" >https://pubs.acs.org/doi/10.1021/acsami.0c12293</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acsami.0c12293" target="_blank" >10.1021/acsami.0c12293</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Transferring lithium ions in the nanochannels of flexible metal-organic frameworks featuring superchaotropic metallacarborane guests: mechanism of ionic conductivity at atomic resolution

Popis výsledku v původním jazyce

Metal–organic frameworks (MOFs), owing to their unique architecture, attract consistent attention in the design of high-performance Li battery materials. Here, we report a new category of ion-conducting crystalline materials for all-solid-state electrolytes based on an MIL53(Al) framework featuring a superchaotropic metallacarborane (Li+CoD–) salt and present the first quantitative data on Li+ ion sites, local dynamics, chemical exchange, and the formation of charge-transfer pathways. We used multinuclear solid-state nuclear magnetic resonance (ss-NMR) spectroscopy to examine the mechanism of ionic conductivity at atomic resolution and to elucidate order–disorder processes, framework–ion interactions, and framework breathing during the loading of Li+CoD– species and transfer of Li+ ions. In this way, the MIL53(Al)@LiCoD framework was found to adopt an open-pore conformation accompanied by a minor fraction of narrow-pore channels. The inserted Li+ ions have two states (free and bound), which both exhibit extensive motions. Both types of Li+ ions form mutually communicating chains, which are large enough to enable efficient long-range charge transfer and macroscopic conductivity. The superchaotropic anions undergo high-amplitude uniaxial rotation motions supporting the transfer of Li+ cations along them, while the fluctuations of MOF aromatic linkers support the penetration of Li+ through the channel walls. Our findings provide a detailed atomic-resolution insight into the mechanism of ionic conductivity and thus have significant implications for the design of the next generation of energy-related materials.

Název v anglickém jazyce

Transferring lithium ions in the nanochannels of flexible metal-organic frameworks featuring superchaotropic metallacarborane guests: mechanism of ionic conductivity at atomic resolution

Popis výsledku anglicky

Metal–organic frameworks (MOFs), owing to their unique architecture, attract consistent attention in the design of high-performance Li battery materials. Here, we report a new category of ion-conducting crystalline materials for all-solid-state electrolytes based on an MIL53(Al) framework featuring a superchaotropic metallacarborane (Li+CoD–) salt and present the first quantitative data on Li+ ion sites, local dynamics, chemical exchange, and the formation of charge-transfer pathways. We used multinuclear solid-state nuclear magnetic resonance (ss-NMR) spectroscopy to examine the mechanism of ionic conductivity at atomic resolution and to elucidate order–disorder processes, framework–ion interactions, and framework breathing during the loading of Li+CoD– species and transfer of Li+ ions. In this way, the MIL53(Al)@LiCoD framework was found to adopt an open-pore conformation accompanied by a minor fraction of narrow-pore channels. The inserted Li+ ions have two states (free and bound), which both exhibit extensive motions. Both types of Li+ ions form mutually communicating chains, which are large enough to enable efficient long-range charge transfer and macroscopic conductivity. The superchaotropic anions undergo high-amplitude uniaxial rotation motions supporting the transfer of Li+ cations along them, while the fluctuations of MOF aromatic linkers support the penetration of Li+ through the channel walls. Our findings provide a detailed atomic-resolution insight into the mechanism of ionic conductivity and thus have significant implications for the design of the next generation of energy-related materials.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10404 - Polymer science

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

ACS Applied Materials and Interfaces

ISSN

1944-8244

e-ISSN

—

Svazek periodika

12

Číslo periodika v rámci svazku

42

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

47447-47456

Kód UT WoS článku

000584489800029

EID výsledku v databázi Scopus

2-s2.0-85094219898