TY - JOUR
T1 - Stabilizing Crystal Framework of an Overlithiated Li1+xMn2O4 Cathode by Heterointerfacial Epitaxial Strain for High-Performance Microbatteries
AU - Zheng, Jie
AU - Xia, Rui
AU - Baiju, Sourav
AU - Sun, Zixiong
AU - Kaghazchi, Payam
AU - ten Elshof, Johan E.
AU - Koster, Gertjan
AU - Huijben, Mark
N1 - Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/12/13
Y1 - 2023/12/13
N2 - To meet the increasing demands of high-energy and high-power-density lithium-ion microbatteries, overlithiated Li1+xMn2O4 (0 ≤ x ≤ 1) is an attractive cathode candidate due to the high theoretical capacity of 296 mAh g-1 and the interconnected lithium-ion diffusion pathways. However, overlithiation triggers the irreversible cubic-tetragonal phase transition due to Jahn-Teller distortion, causing rapid capacity degradation. In contrast to conventional lithium-ion batteries, microbatteries offer the opportunity to develop specific thin-film-based modification strategies. Here, heterointerfacial lattice strain is proposed to stabilize the spinel crystal framework of an overlithiated Li1+xMn2O4 (LMO) cathode by epitaxial thin film growth on an underlying SrRuO3 (SRO) electronic conductor layer. It is demonstrated that the lattice misfit at the LMO/SRO heterointerface results in an in-plane epitaxial constraint in the full LMO film. This suppresses the lattice expansion during overlithiation that typically occurs in the in-plane direction. It is proposed by density functional theory modeling that the epitaxial constraint can accommodate the internal lattice stress originating from the cubic-tetragonal transition during overlithiation. As a result, a doubling of the capacity is achieved by reversibly intercalating a second lithium ion in a LiMn2O4 epitaxial cathode with a complete reversible phase transition. An impressive cycling stability can be obtained with reversible capacity retentions of above 90.3 and 77.4% for the 4 and 3 V range, respectively. This provides an effective strategy toward a stable overlithiated Li1+xMn2O4 epitaxial cathode for high-performance microbatteries.
AB - To meet the increasing demands of high-energy and high-power-density lithium-ion microbatteries, overlithiated Li1+xMn2O4 (0 ≤ x ≤ 1) is an attractive cathode candidate due to the high theoretical capacity of 296 mAh g-1 and the interconnected lithium-ion diffusion pathways. However, overlithiation triggers the irreversible cubic-tetragonal phase transition due to Jahn-Teller distortion, causing rapid capacity degradation. In contrast to conventional lithium-ion batteries, microbatteries offer the opportunity to develop specific thin-film-based modification strategies. Here, heterointerfacial lattice strain is proposed to stabilize the spinel crystal framework of an overlithiated Li1+xMn2O4 (LMO) cathode by epitaxial thin film growth on an underlying SrRuO3 (SRO) electronic conductor layer. It is demonstrated that the lattice misfit at the LMO/SRO heterointerface results in an in-plane epitaxial constraint in the full LMO film. This suppresses the lattice expansion during overlithiation that typically occurs in the in-plane direction. It is proposed by density functional theory modeling that the epitaxial constraint can accommodate the internal lattice stress originating from the cubic-tetragonal transition during overlithiation. As a result, a doubling of the capacity is achieved by reversibly intercalating a second lithium ion in a LiMn2O4 epitaxial cathode with a complete reversible phase transition. An impressive cycling stability can be obtained with reversible capacity retentions of above 90.3 and 77.4% for the 4 and 3 V range, respectively. This provides an effective strategy toward a stable overlithiated Li1+xMn2O4 epitaxial cathode for high-performance microbatteries.
KW - Epitaxial stabilization
KW - Jahn−Teller distortion
KW - Lithium-ion microbatteries
KW - Overlithiated LiMnO
KW - Spinel cathode
KW - Thin film
KW - UT-Hybrid-D
UR - http://www.scopus.com/inward/record.url?scp=85180980427&partnerID=8YFLogxK
U2 - 10.1021/acsnano.3c08849
DO - 10.1021/acsnano.3c08849
M3 - Article
C2 - 38088313
AN - SCOPUS:85180980427
SN - 1936-0851
VL - 17
SP - 25391
EP - 25404
JO - ACS nano
JF - ACS nano
IS - 24
ER -