Dynamic Structure Evolution of Extensively Delithiated High Voltage Spinel Li1+xNi0.5Mn1.5O4x < 1.5

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389005%3A_____%2F23%3A00570288" target="_blank" >RIV/61389005:_____/23:00570288 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1021/jacs.2c09621" target="_blank" >https://doi.org/10.1021/jacs.2c09621</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.2c09621" target="_blank" >10.1021/jacs.2c09621</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Dynamic Structure Evolution of Extensively Delithiated High Voltage Spinel Li1+xNi0.5Mn1.5O4x < 1.5

Popis výsledku v původním jazyce

High voltage spinel is one of the most promising next-generation cobalt-free cathode materials for lithium ion battery applications. Besides the typically utilized compositional range of LixNi0.5Mn1.5O4 0 < x < 1 in the voltage window of 4.90-3.00 V, additional 1.5 mol of Li per formula unit can be introduced into the structure, in an extended voltage range to 1.50 V. Theoretically, this leads to significant increase of the specific energy from 690 to 1190 Wh/kg. However, utilization of the extended potential window leads to rapid capacity fading and voltage polarization that lack a comprehensive explanation. In this work, we conducted potentiostatic entropymetry, operando XRD and neutron diffraction on the ordered stoichiometric spinel LixNi0.5Mn1.5O4 within 0 < x < 2.5 in order to understand the dynamic structure evolution and correlate it with the voltage profile. During the two-phase reaction from cubic (x < 1) to tetragonal (x > 1) phase at similar to 2.8 V, we identified the evolution of a second tetragonal phase with x > 2. The structural evaluation during the delithiation indicates the formation of an intermediate phase with cubic symmetry at a lithium content of x = 1.5. Evaluation of neutron diffraction data, with maximum entropy method, of the highly lithiated phase LixNi0.5Mn1.5O4 with 2 < x < 2.5 strongly suggests that lithium ions are located on octahedral 8a and tetrahedral 4a positions of the distorted tetragonal phase I41amd. Consequently, we were able to provide a conclusive explanation for the additional voltage step at 2.10 V, the sloping voltage profile below 1.80 V, and the additional voltage step at similar to 3.80 V.

Název v anglickém jazyce

Dynamic Structure Evolution of Extensively Delithiated High Voltage Spinel Li1+xNi0.5Mn1.5O4x < 1.5

Popis výsledku anglicky

High voltage spinel is one of the most promising next-generation cobalt-free cathode materials for lithium ion battery applications. Besides the typically utilized compositional range of LixNi0.5Mn1.5O4 0 < x < 1 in the voltage window of 4.90-3.00 V, additional 1.5 mol of Li per formula unit can be introduced into the structure, in an extended voltage range to 1.50 V. Theoretically, this leads to significant increase of the specific energy from 690 to 1190 Wh/kg. However, utilization of the extended potential window leads to rapid capacity fading and voltage polarization that lack a comprehensive explanation. In this work, we conducted potentiostatic entropymetry, operando XRD and neutron diffraction on the ordered stoichiometric spinel LixNi0.5Mn1.5O4 within 0 < x < 2.5 in order to understand the dynamic structure evolution and correlate it with the voltage profile. During the two-phase reaction from cubic (x < 1) to tetragonal (x > 1) phase at similar to 2.8 V, we identified the evolution of a second tetragonal phase with x > 2. The structural evaluation during the delithiation indicates the formation of an intermediate phase with cubic symmetry at a lithium content of x = 1.5. Evaluation of neutron diffraction data, with maximum entropy method, of the highly lithiated phase LixNi0.5Mn1.5O4 with 2 < x < 2.5 strongly suggests that lithium ions are located on octahedral 8a and tetrahedral 4a positions of the distorted tetragonal phase I41amd. Consequently, we were able to provide a conclusive explanation for the additional voltage step at 2.10 V, the sloping voltage profile below 1.80 V, and the additional voltage step at similar to 3.80 V.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

20501 - Materials engineering

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

1520-5126

Svazek periodika

145

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

4450-4461

Kód UT WoS článku

000935511800001

EID výsledku v databázi Scopus

2-s2.0-85148421748