TY - JOUR
T1 - Enhanced Lithium Transport by Control of Crystal Orientation in Spinel LiMn2O4 Thin Film Cathodes
AU - Hendriks, R.
AU - Cunha, D.M.
AU - Singh, D.P.
AU - Huijben, M.
PY - 2018/12/24
Y1 - 2018/12/24
N2 - A promising cathode material for rechargeable batteries is LiMn2O4, which exhibits higher operating voltage, reduced toxicity and lower costs as compared to commonly used LiCoO2 cathodes. However, LiMn2O4 suffers from limited cycle life, as excessive capacity fading occurs during battery cycling due to dissolution of Mn into the acidic electrolyte. Here, we show that by structural engineering of stable, epitaxial LiMn2O4 thin films the electrochemical properties can be enhanced as compared to polycrystalline samples. Control of the specific crystal orientation of the LiMn2O4 thin films resulted in dramatic differences in surface morphology with pyramidal, rooftop or flat features for respectively (100), (110), and (111) orientations. All three types of LiMn2O4 films expose predominantly ⟨111⟩ crystal facets, which is the lowest energy state surface for this spinel structure. The (100)-oriented LiMn2O4 films exhibited the highest capacities and (dis)charging rates up to 33C, and good cyclability over a thousand cycles, demonstrating enhanced cycle life without excessive capacity fading as compared to previous polycrystalline studies.
AB - A promising cathode material for rechargeable batteries is LiMn2O4, which exhibits higher operating voltage, reduced toxicity and lower costs as compared to commonly used LiCoO2 cathodes. However, LiMn2O4 suffers from limited cycle life, as excessive capacity fading occurs during battery cycling due to dissolution of Mn into the acidic electrolyte. Here, we show that by structural engineering of stable, epitaxial LiMn2O4 thin films the electrochemical properties can be enhanced as compared to polycrystalline samples. Control of the specific crystal orientation of the LiMn2O4 thin films resulted in dramatic differences in surface morphology with pyramidal, rooftop or flat features for respectively (100), (110), and (111) orientations. All three types of LiMn2O4 films expose predominantly ⟨111⟩ crystal facets, which is the lowest energy state surface for this spinel structure. The (100)-oriented LiMn2O4 films exhibited the highest capacities and (dis)charging rates up to 33C, and good cyclability over a thousand cycles, demonstrating enhanced cycle life without excessive capacity fading as compared to previous polycrystalline studies.
UR - http://www.scopus.com/inward/record.url?eid=2-s2.0-85064114907&partnerID=MN8TOARS
U2 - 10.1021/acsaem.8b01477
DO - 10.1021/acsaem.8b01477
M3 - Article
SN - 2574-0962
VL - 1
SP - 7046
EP - 7051
JO - ACS Applied Energy Materials
JF - ACS Applied Energy Materials
IS - 12
ER -